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Characteristics and environmental aspects of slag: a review

Slag is a waste product from the pyrometallurgical processing of various ores. Based on over 150 published studies, this paper provides an overview of mineralogical and geochemical characteristics of different types of slag and their environmental consequences, particularly from the release of potentially toxic elements to water. This chapter reviews the characteristics of both ferrous (steel and blast furnace Fe) and non-ferrous (Ag, Cu, Ni, Pb, Sn, Zn) slag. Interest in slag has been increasing steadily as large volumes, on the order of hundreds of millions of tonnes, are produced annually worldwide. Research on slag generally focuses on potential environmental issues related to the weathering of slag dumps or on its utility as a construction material or reprocessing for secondary metal recovery. The chemistry and mineralogy of slag depend on the metallurgical processes that create the material and will influence its fate as waste or as a reusable product. The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO 2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.

Applied Geochemistry↗

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in δ 65 Cu (− 1.41 to + 0.30‰), δ 56 Fe (− 0.56 to + 0.34‰), and δ 66 Zn (0.31 to 0.49‰) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Chemical 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↗

Mineralogy and geochemistry of boehmite-rich coals: New insights from the Haerwusu Surface Mine, Jungar Coalfield, Inner Mongolia, China

Boehmite-rich coal of Pennsylvanian age was discovered earlier at the Heidaigou Surface Mine, Jungar Coalfield, Inner Mongolia, China. This paper reports new results on 29 bench samples of the no. 6 coal from a drill core from the adjacent Haerwusu Surface Mine, and provides new insights into the origin of the minerals and elements present. The results show that the proportion of inertinite in the no. 6 coal is higher than in other Late Paleozoic coals in northern China. Based on mineral proportions (boehmite to kaolinite ratio) and major element concentrations in the coal benches of the drill core, the no. 6 coal may be divided into five sections (I to V). Major minerals in Sections I and V are kaolinite. Sections II and IV are mainly kaolinite with a trace of boehmite, and Section III is high in boehmite. The boehmite is derived from bauxite in the weathered surface (Benxi Formation) in the sediment-source region. The no. 6 coal is rich in Al2O3 (8.89%), TiO2 (0.47%), Li (116????g/g), F (286????g/g), Ga (18????g/g), Se (6.1????g/g), Sr (350????g/g), Zr (268????g/g), REEs (172????g/g), Pb (30????g/g), and Th (17????g/g). The elements are classified into five associations by cluster analysis, i.e. Groups A, B, C, D, and E. Group A (ash-SiO2-Al2O3-Na2O-Li) and Group B (REE-Sc-In-Y-K2O-Rb-Zr-Hf-Cs-U-P2O5-Sr-Ba-Ge) are strongly correlated with ash yield and mainly have an inorganic affinity. The elements that are negatively or less strongly correlated with ash yield (with exceptions of Fe2O3, Be, V, and Ni) are grouped in the remaining three associations: Group C, Se-Pb-Hg-Th-TiO2-Bi-Nb-Ta-Cd-Sn; Group D, Co-Mo-Tl-Be-Ni-Sb-MgO-Re-Ga-W-Zn-V-Cr-F-Cu; and Group E, S-As-CaO-MnO-Fe2O3. Aluminum is mainly distributed in boehmite, followed by kaolinite. The high correlation coefficients of the Li-ash, Li-Al2O3, and Li-SiO2 pairs indicate that Li is related to the aluminosilicates in the coal. The boehmite-rich coal is high in gallium and F, which occur in boehmite and the organic matter. Selenium and Pb are mainly in epigenetic clausthalite fillings in fractures. The abundant rare earth elements in the coal benches were supplied from two sources: the bauxite on the weathered surface of the Benxi Formation and from adjacent partings by groundwater leaching during diagenesis. The light rare earth elements (LREEs) are more easily leached from the partings and incorporated into the organic matter than the heavy REEs, leading to a higher ratio of LREEs to HREEs in the coal benches than in the overlying partings. ?? 2008 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↗

Geochemistry of hydrothermal alteration at the Qolqoleh gold deposit, northern Sanandaj–Sirjan metamorphic belt, northwestern Iran: Vectors to high-grade ore bodies

The Qolqoleh orogenic gold deposit in the northern part of the Sanandaj–Sirjan metamorphic belt in northwestern Iran is hosted by a steeply dipping sequence of greenschist facies Cretaceous volcano–sedimentary rocks, including mafic to intermediate metavolcanic rocks, sericite and chlorite schist, and marble. Geochemical and petrochemical data including the ∑ REE, (La/Yb) N and Eu/Eu* ratios were obtained from country rocks, ore-enveloping alteration zones, and mineralized zones to assess the nature of the trace element and rare earth element (REE) interaction between the wall rock and the mineralizing fluid. Quartz–sulfide veins at the deposit are characterized by a pyrite–pyrrhotite–chalcopyrite–sphalerite–arsenopyrite–native gold assemblage. Alteration halos border the mineralized zones and broadly comprise: (1) an outer carbonate–chlorite alteration zone in all rock types, particularly in chlorite schist; (2) a middle sericite–carbonate alteration zone in the sericite schist; and (3) an inner quartz–sulfide alteration zone in sericite schist and mafic to intermediate metavolcanic rocks. The geochemical data indicate that the concentrations of Al 2 O 3 , P 2 O 5 , TiO 2 , Y, and Zr are relatively constant, suggesting that these elements were the least mobile during hydrothermal activity. Using Al 2 O 3 as the immobile component, there is evidence for mobility of trace elements, particularly light REE, TiO 2 , and Zr in the altered wall rocks. The altered rocks show a relatively light REE depletion ((La/Yb) N ≅ 9.41), which clearly correlates with the grades of gold mineralization and intensity of the alteration (3 ppm Au). The depletion of light REE is best indicated by a decrease in (La/Yb) N as shown by ratios of 10.5 to 11.8. Wall rock decarbonation reactions during infiltration of the mineralizing fluid resulted in differential mobilization of REE, from a fluid with initially low REE content. The overall trace element geochemistry of the altered wall rock is controlled by the initial composition of the wall rocks and the ore-fluid composition. Hydrothermal ore-forming fluids are recognized as CO 2 -rich near-neutral reduced fluids with high values of H 2 S, K, and S content. Observed variability in alteration halos at the Qolqoleh deposit points to major differences in REE and trace element content in original host rocks that have interacted with a relatively similar ore fluid. Therefore, depending on the composition of each host rock lithology, the geochemistry of hydrothermal alteration (e.g., ∑ REE content and (La/Yb) N ratios) and alteration mineralogy including the carbonate–sericite–quartz–sulfide assemblages may be used as a primary tool for lithogeochemical exploration for gold deposits in northwestern Iran.

Journal of Geochemical Exploration↗

Assessment of resource potential from mine tailings using geostatistical modeling for compositions: A methodology and application to Katherine Mine site, Arizona, USA

The mining industry, in most cases, targets a specific valuable commodity that is present in small quantities within large volumes of extracted material. After milling and processing, most of the extracted material and the effluents are stored as waste (tailings) in impoundments, such as dams or waste dumps, or are backfilled into underground mines. In time, tailing materials may become an issue of environmental and health concern due to the hazardous elements, ions, and oxides contained within the waste material. In addition, handling and storage of such waste in dams may pose the risk of dam failure with catastrophic consequences to nature and nearby communities. On the other hand, tailings may offer potential as secondary sources of critical elements (CEs), including rare earth elements (REEs), which may have been overlooked during primary production and processing. Therefore, treating mine tailings as a resource has economic and environmental benefits by reducing the waste from new and historical mine sites through remining. One of the critical steps for taking advantage of these benefits is to spatially quantify the resources and the pollutants, which require the application of adequate data analysis and modeling methods, often to compositional geochemical data. Utilizing adequate methods is especially important for correctly quantifying resource potential, as the quantities will often be at low concentrations. This work presents quantification of resource potential (Au, Ag, Cu, Zn, Pb) and elements of environmental concern (Hg and As) from the tailings of a historic mine site, Katherine Mine, AZ, USA. Data reported by the U.S. Bureau of Mines (USBM) after extensive field campaigns in the 1990s, including sampling from tailing impoundment and surrounding areas for geochemical characterization and geophysical surveys, were used. First, compositional data (CoDa) analysis was employed to explore associations of sampling locations, geochemical parts, and the clustering of samples. Next, sequential Gaussian simulation (SGSIM) was applied to samples that showed a genetic link to tailing material after isometric log-ratio transformation (ilr) and mix/max autocorrelation factor (MAF) transformation for spatial modeling and uncertainty evaluation. Geostatistical results revealed spatial variability of concentrations within the tailing area. Uncertainty evaluation based on realizations indicated that Cu (14.27–20.01 t), Zn (44.23–76.23 t), and Pb (22.56–38.28 t) are the most abundant elements within a 5 %–95 % interval, followed by Ag and Au (~5.3 and 0.18 t, at 50th percentile), respectively. Of the elements of health concern, As was found to be ~4.8 t (50th percentile) in the tailing area. The work also showed that ~0.51 t As, 0.005 t Hg, 0.020 t of Au, and 0.62 t of Ag were carried to Lake Mohave by an ephemeral stream called Katherine Wash, which transects the tailings.

Arizona↗

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element. We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases. Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO 2 , carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO 2 . Thermodynamic calculations indicate that Te occurs predominantly as H 5 TeO 6 − in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO 2 in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.

Geochimica et Cosmochimica Acta↗

Stratigraphy, geochemistry and tectonic significance of the Oligocene magmatic rocks of western Oaxaca, southern Mexico

In Western Oaxaca, Tertiary magmatic activity is represented by extensive plutons along the continental margin and volcanic sequences in the inland region. K-Ar age determinations reported previously and in the present work indicate that these rocks correspond to a relatively broad arc in this region that was active mainly during the Oligocene (~ 35 to ~ 25 Ma). In the northern sector of western Oaxaca (Huajuapan-Monte Verde-Yanhuitlan), the volcanic suite comprises principally basaltic andesite to andesitic lavas, overlying minor silicic to intermediate volcaniclastic rocks (epiclastic deposits, ash fall tuffs, ignimbrites) that were deposited in the lacustrine-fluvial environment. The southern sector of the volcanic zone includes the Tlaxiaco-Laguna de Guadalupe region and consists of intermediate to silicic pyroclastic and epiclastic deposits, with silicic ash fall tuffs and ignimbrites. In both sectors, numerous andesitic to dacitic hypabyssal intrusions (stocks and dikes) were emplaced at different levels of the sequence. The granitoids of the coastal plutonic belt are generally more differentiated than the volcanic rocks that predominate in the northern sector and vary in composition from granite to granodiorite. The studied rocks show large-ion lithophile element (LILE) enrichment (K, Rb, Ba, Th) relative to high-field-strength (HFS) elements (Nb, Ti, Zr) that is characteristic of subduction-related magmatic rocks. On chondrite-normalized rare earth element diagrams, these samples display light rare earth element enrichment (LREE) and a flat pattern for the heavy rare earth elements (HREE). In spite of the contrasting degree of differentiation between the coastal plutons and inland volcanic rocks, there is a relatively small variation in the isotopic composition of these two suites. Initial 87Sr/86Sr ratios obtained and reported previously for Tertiary plutonic rocks of western Oaxaca range from 0.7042 to 0.7054 and ??Nd values, from -3.0 to +2.4, and for the volcanic rocks, from 0.7042 to 0.7046 and 0 +2.6. The range of these isotope ratios and those reported for the basement rocks in this region suggest a relatively low degree of old crustal involvement for most of the studied rocks. The Pb isotopic compositions of the Tertiary magmatic rocks also show a narrow range [(206Pb/204Pb) = 18.67-18.75; (207Pb/204Pb) = 15.59-15.62; (208Pb/204Pb) = 38.44-38.59], suggesting a similar source region for the volcanic and plutonic rocks. Trace elements and isotopic compositions suggest a mantle source in the subcontinental lithosphere that has been enriched by a subduction component. General tectonic features in this region indicate a more active rate of transtensional deformation for the inland volcanic region than along the coastal margin during the main events of Oligocene magmatism. The lower degree of differentiation of the inland volcanic sequences, particularly the upper unit of the northern sector, compared to the plutons of the coastal margin, suggests that the differentiation of the Tertiary magmas in southern Mexico was controlled to a great extent by the characteristics of the different strain domains. (C) 2000 Elsevier Science B.V. All rights reserved.

Conference Paper↗

Multivariate analyses of Erzgebirge granite and rhyolite composition: Implications for classification of granites and their genetic relations

High-precision major, minor and trace element analyses for 44 elements have been made of 329 Late Variscan granitic and rhyolitic rocks from the Erzgebirge metallogenic province of Germany. The intrusive histories of some of these granites are not completely understood and exposures of rock are not adequate to resolve relationships between what apparently are different plutons. Therefore, it is necessary to turn to chemical analyses to decipher the evolution of the plutons and their relationships. A new classification of Erzgebirge plutons into five major groups of granites, based on petrologic interpretations of geochemical and mineralogical relationships (low-F biotite granites; low-F two-mica granites; high-F, high-P2O5 Li-mica granites; high-F, low-P2O5 Li-mica granites; high-F, low-P2O5 biotite granites) was tested by multivariate techniques. Canonical analyses of major elements, minor elements, trace elements and ratio variables all distinguish the groups with differing amounts of success. Univariate ANOVA's, in combination with forward-stepwise and backward-elimination canonical analyses, were used to select ten variables which were most effective in distinguishing groups. In a biplot, groups form distinct clusters roughly arranged along a quadratic path. Within groups, individual plutons tend to be arranged in patterns possibly reflecting granitic evolution. Canonical functions were used to classify samples of rhyolites of unknown association into the five groups. Another canonical analysis was based on ten elements traditionally used in petrology and which were important in the new classification of granites. Their biplot pattern is similar to that from statistically chosen variables but less effective at distinguishing the five groups of granites. This study shows that multivariate statistical techniques can provide significant insight into problems of granitic petrogenesis and may be superior to conventional procedures for petrological interpretation.

Computers & Geosciences↗

The types of data needed for assessing the environmental and human health impacts of coal

Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.

International Journal of Coal Geology↗

Genetic features of petroleum systems in rift basins of eastern China

Most oil-bearing basins in eastern China are Mesozoic-Cenozoic continental rifts which have played a habitat for oil and gas in China. Investigation of the petroleum systems may give a better understanding of the oil and gas habitats in these basins. Of the essential elements of the petroleum system, the source rock is the most important in rift basins. However, rift tectonic evolution controls all the essential elements and processes nevessary for a petroleum system. A four stage evolution model is suggested for the controls in the rift basin. A rift basin may consist of sub-basins, depressions, sub-depressions, and major, moderate, and minor uplifts. A depression or sub-depression has its own depocentre (mainly occupied by source rock) and all kinds of lacustrine sediments, and thus has all the essential elements of a petroleum system. However, only those depressions or sub-depressions which are rich in organic matter and deeply buried to generate oil and gas form petroleum systems. Immature oil, another characteristic, complicates the petroleum system in the rift basins. Three types of oil and gas habitats are described as a result of this analysis of the petroleum systems of the 26 largest oil and gas fields discovered in eastern China rift basins: uplifts between oil source centres are the most prospective areas for oil and gas accumulations, slopes connecting oil source centres and uplifts are the second, and the third type is subtle traps in the soil source centre.Most oil-bearing basins in eastern China are Mesozoic-Cenozoic continental rifts which have played a habitat for oil and gas in China. Investigation of the petroleum systems may give a better understanding of the oil and gas habitats in these basins. Of the essential elements of the petroleum system, the source rock is the most important in rift basins. However, rift tectonic evolution controls all the essential elements and processes necessary for a petroleum system. A four stage evolution model is suggested for the controls in the rift basin. A rift basin may consist of sub-basins, depressions, sub-depressions, and major, moderate, and minor uplifts. A depression or sub-depression has its own depocentre (mainly occupied by source rock) and all kinds of lacustrine sediments, and thus has all the essential elements of a petroleum system. However, only those depressions or sub-depressions which are rich in organic matter and deeply buried to generate oil and gas form petroleum systems. Immature oil, another characteristic, complicates the petroleum system in the rift basins. Three types of oil and gas habitats are described as a result of this analysis of the petroleum systems of the 26 largest oil and gas fields discovered in eastern China rift basins: uplifts between oil source centres are the most prospective areas for oil and gas accumulations, slopes connecting oil source centres and uplifts are the second, and the third type is subtle traps in the oil source centre.

Marine and Petroleum Geology↗

Petrology and geochemistry of late-stage intrusions of the A-type, mid-Proterozoic Pikes Peak batholith (Central Colorado, USA): Implications for petrogenetic models

The ~1.08 Ga anorogenic, A-type Pikes Peak batholith (Front Range, central Colorado) is dominated by coarse-grained, biotite ?? amphibole syenogranites and minor monzogranites, collectively referred to as Pikes Peak granite (PPG). The batholith is also host to numerous small, late-stage plutons that have been subdivided into two groups (e.g. Wobus, 1976. Studies in Colorado Field Geology, Colorado School of Mines Professional Contributions, Colorado): (1) a sodic series (SiO2= ~44-78 wt%; K/Na=0.32-1.36) composed of gabbro, diabase, syenite/quartz syenite and fayalite and sodic amphibole granite; and (2) a potassic series (SiO2= ~ 70-77 wt%; K/Na=0.95-2.05), composed of biotite granite and minor quartz monzonite. Differences in major and trace element and Nd isotopic characteristics for the two series indicate different petrogenetic histories. Potassic granites of the late-stage intrusions appear to represent crustal anatectic melts derived from tonalite sources, based on comparison of their major element compositions with experimental melt products. In addition, Nd isotopic characteristics of the potassic granites [??(Nd)(1.08 Ga) = -0.2 to -2.7] overlap with those for tonalites/granodiorites [ca 1.7 Ga Boulder Creek intrusions; ??(Nd)(1.08 Ga) = -2.4 to -3.6] exposed in the region. Some of the partial melts evolved by fractionation dominated by feldspar. The late-stage potassic granites share geochemical characteristics with most of the PPG, which is also interpreted to have an anatectic origin involving tonalitic crust. The origin of monzogranites associated with the PPG remains unclear, but mixing between granitic and mafic or intermediate magmas is a possibility. Syenites and granites of the sodic series cannot be explained as crustal melts, but are interpreted as fractionation products of mantle-derived mafic magmas with minor crustal input. High temperature and low oxygen fugacity estimates (e.g. Frost et al., 1988. American Mineralogist 73, 727-740) support a basalt fractionation origin, as do ??(Nd) values for sodic granitoids [??(Nd)(1.08 Ga) = +2.2 to -0.7], which are higher than ??(Nd) values for Colorado crust at 1.08 Ga (ca -1.0 to -4.0). Enrichments in incompatible elements (e.g. rare earth elements, Rb, Y) and depletions in compatible elements (e.g. Cr, Sr, Ba) in the sodic granitoids compared to coeval mafic rocks are also consistent with fractionation. Accessory mineral fractionation, release of fluorine-rich volatiles and/or removal of pegmatitic fluids could have modified abundances of Ce, Nb, Zr and Y in some sodic granitoid magmas. Gabbros and mafic dikes associated with the sodic granitoids have ??(Nd)(1.08 Ga) of -3.0 to +3.5, which are lower than depleted mantle at 1.08 Ga, and their trace element characteristics suggest derivation from mantle sources that were previously affected by subduction-related processes. However, it is difficult to characterize the mantle component in these magmas, because assimilation of crust during magma ascent could also result in their observed geochemical features. The Pikes Peak batholith is composed of at least two petrogenetically different granite types, both of which exhibit geochemical characteristics typical of A-type granites. Models proposed for the petrogenesis of the granitoids imply the existence of mafic rocks at depth and addition of juvenile material to the crust in central Colorado at ~ 1.1 Ga.

Precambrian Research↗

Chapter 4 The meade peak member of the phosphoria formation: Temporal and spatial variations in sediment geochemistry

Variations in the geochemistry of rocks from the Meade Peak Member of the Phosphoria Formation were examined using ratios of elements associated with either the +terrigenous or marine sediment fractions. Inter-element relationships in the terrigenous fraction appear useful for chemo-stratigraphic correlation. A sharp decrease upsection in K 2 O/AI 2 O 3 ratios occurs in the lower half of all but the most northeasterly section, wherein an offset is still evident in average and minimum values. These offsets correspond closely to the lower Guadalupian Series boundary as defined by conodont zonations, coincident with a change from major low-stand to transgressive conditions. The offsets are possibly the result of increased transport distances or flooding of source areas related to transgres- sion of the Phosphoria sea on the Wyoming shelf. A series of intervals displaying high Fe 2 O 3 /Al 2 O 3 , Ba/Al 2 O 3 and Sc/Al 2 O 3 ratios occur in the upper beds of the easternmost sections. The intervals do not appear to reflect amplified marine signals, but rather the introduction of terrigenous sediment from a secondary source, or, simply, reworking of sediments under higher energy conditions. The westernmost section, presumably repre- senting the deepest parts of the Phosphoria basin, contains intervals with high Ba/Al 2 O 3 . We suggest these horizons represent periods of low sediment accumulation during maxi- mum flooding and high-stand conditions. Inter-element relationships in the marine-derived sediment fraction indicate that bottom waters of the Phosphoria basin were dominantly denitrifying (suboxic). Ratios of Cd and Mo to Zn and Cu closely approach those in modern plankton in most of the sections, implying a major biogenic source for these elements. Exceptions occur through- out the westernmost (distal) section, possibly due to changes in the dominant plankton populations and relative nutrient uptakes, and in the upper part of the most northeasterly (shoreward, ramp) section, which we suggest is due to increased oxygen levels. Relatively thick phosphatic layers occur in basinal areas due largely to lack of terrig- enous dilution during deposition. These basinal deposits appear to have lower concentra- tions of many trace elements than more shoreward deposits. This may reflect deposition away from areas of peak primary production. Alternatively, biogenic detritus in these areas may have been derived from differing populations of primary producers with differing nutrient requirements. Both mid-shelf (middle ramp) and marginal environments were sites of accumulation of rich phosphatic units with high concentrations of trace elements. Deposits from marginal areas have the most varied geochemistry, largely because they experienced greater variability in terrigenous sediment influx. Even moderate changes in sea level may have dramatically altered energy levels, sediment mixing, and the amount of organic detritus reaching the sediment surface in these shallower marginal areas.

Colorado, Idaho, Montana, Nebraska, North Dakota, ↗

Effects of sulfur impregnation temperature on the properties and mercury adsorption capacities of activated carbon fibers (ACFs)

Laboratory studies were conducted to determine the role of sulfur functional groups and micropore surface area of carbon-based adsorbents on the adsorption of Hg0 from simulated coal combustion flue gases. In this study, raw activated carbon fibers that are microporous (ACF-20) were impregnated with elemental sulfur between 250 and 650 ??C. The resulting samples were saturated with respect to sulfur content. Total sulfur content of the sulfur impregnated ACF samples decreased with increasing impregnation temperatures from 250 and 500 ??C and then remained constant to 650 ??C. Results from sulfur K-edge X-ray absorption near-edge structure (S-XANES) spectroscopy showed that sulfur impregnated on the ACF samples was in both elemental and organic forms. As sulfur impregnation temperature increased, however, the relative amounts of elemental sulfur decreased with a concomitant increase in the amount of organic sulfur. Thermal analyses and mass spectrometry revealed that sulfur functional groups formed at higher impregnation temperatures were more thermally stable. In general, sulfur impregnation decreased surface area and increased equilibrium Hg0 adsorption capacity when compared to the raw ACF sample. The ACF sample treated with sulfur at 400 ??C had a surface area of only 94 m2/g compared to the raw ACF sample's surface area of 1971 m2/g, but at least 86% of this sample's surface area existed as micropores and it had the largest equilibrium Hg0adsorption capacities (2211-11343 ??g/g). Such a result indicates that 400 ??C is potentially an optimal sulfur impregnation temperature for this ACF. Sulfur impregnated on the ACF that was treated at 400 ??C was in both elemental and organic forms. Thermal analyses and CS2extraction tests suggested that elemental sulfur was the main form of sulfur affecting the Hg0 adsorption capacity. These findings indicate that both the presence of elemental sulfur on the adsorbent and a microporous structure are important properties for improving the performance of carbon-based adsorbents for the removal of Hg0 from coal combustion flue gases.

Environmental Science & Technology↗

Geochemical surveys in the United States in relation to health.

Geochemical surveys in relation to health may be classified as having one, two or three dimensions. One-dimensional surveys examine relations between concentrations of elements such as Pb in soils and other media and burdens of the same elements in humans, at a given time. The spatial distributions of element concentrations are not investigated. The primary objective of two-dimensional surveys is to map the distributions of element concentrations, commonly according to stratified random sampling designs based on either conceptual landscape units or artificial sampling strata, but systematic sampling intervals have also been used. Political units have defined sample areas that coincide with the units used to accumulate epidemiological data. Element concentrations affected by point sources have also been mapped. Background values, location of natural or technological anomalies and the geographic scale of variation for several elements often are determined. Three-dimensional surveys result when two-dimensional surveys are repeated to detect environmental changes. -Author

Philosophical Transactions of the Royal Society B:↗

Distribution and grain-size partitioning of metals in bovfom sediments of an experimentally acidified Wisconsin lake

A study of concentrations and distribution of major and trace elements in surficial bottom sediments of Little Rock Lake in northern Wisconsin included examination of spatial variation and grain-size effects. No significant differences with respect to metal distribution in sediments were observed between the two basins of the lake, despite the experimental acidification of one of the basins from pH 6.1 to 4.6. The concentrations of most elements in the lake sediments were generally similar to soil concentrations in the area and were well below sediment quality criteria. Two exceptions were lead and zinc, whose concentrations in July 1990 exceeded the criteria of 50 μg/g and 100 μg/g, respectively, in both littoral and pelagic sediments. Concentrations of some elements, particularly Cu, Pb, and Zn, increased along transects from nearshore to midlake, following a similar gradient of sedimentary organic carbon. In contrast, Mn, Fe, and alkali/alkaline-earth elements were at maximum concentrations in nearshore sediments. These elements are less likely to partition to organic particles, and their distribution is more dependent on mineralogical composition, grain size, and other factors. Element concentrations varied among different sediment grain-size fractions, although a simple inverse relation to grain size was not observed. Fe, Mn, Pb, and Zn were more concentrated in a grain-size range 20–60 tm than in either the very fine or the coarse fractions, possibly because of the aggregation of smaller particles cemented together by organic and Fe/Mn hydrous-oxide coatings.

Wisconsin↗

History of the Redwall Limestone of northern Arizona

Throughout most of northern Arizona the Redwall Limestone of Mississippian age is readily divisible into four lithologic units, designated in ascending order as the Whitmore Wash, Thunder Springs, Mooney Falls, and Horseshoe Mesa Members. The first and third members are thick-bedded to massive carbonate rock. The Horseshoe Mesa Member is relatively thin-bedded limestone, and the Thunder Springs Member is distinctive because it consists of chert beds alternating with thin beds of carbonate rock. Trends in thickness of the various members indicate that the sediment that formed the Redwall was deposited on an even, gently sloping shelf that extended westward from the Defiance positive element, a low landmass located near the present eastern border of northern Arizona. The Peach Springs and Payson ridges projected west and southwest, respectively, from the positive element. These ridges, which were partly submerged and partly above sea level during Mississippian time, are indicated by the patterns of isopach lines and, in part, by the distribution of faunas. The ridges divided the Arizona section of the shelf into three segments: the northern-most, which slopes northwest toward the Cordilleran geosyncline, and the other two, which slope toward the south and southwest. Two transgressions and two regressions of the western and southern seaways are believed to be represented by the Redwall. The first transgression, which is recorded by thick beds of clastic sediment of the Whitmore Wash Member, was less extensive than the second, which is recorded by massive beds of the Mooney Falls Member, for on the western margins of the Defiance positive element the Mooney Falls Member overlaps the two lower members. Furthermore, south of Grand Canyon the Whitmore Wash and Thunder Springs Members lap against the Payson ridge without covering it, whereas the Mooney Falls Member, although relatively thin, extends across it. Regression is believed to be represented by thin beds of the Thunder Springs and Horseshoe Mesa Members, which are interpreted to be the result of low base level caused by silting up with clastic material and consequent retreat of the sea. Cycles in sedimentation are well developed in some parts of the Redwall, especially in the upper two members in which differences in grain size represent five major cycles recognized throughout the extent of the Grand Canyon. These textural differences, ranging from aphanitic to coarse grained, are considered to be not measures of the amount of transportation, as with terrigenous sediments, but reflections of the degree of turbulence or the lack of turbulence during deposition. They are interpreted as indicators of cyclic fluctuations in environment, probably related to changes in wave base. Several clearly defined facies within the Redwall indicate environments of deposition. The clastic limestone that forms a major part of the formation, especially in the offshore areas to the west and south, is believed to represent normal marine conditions where circulation was good and turbulence moderate to strong. Uniform finely crystalline dolomite probably developed through early diagenetic processes on the sea floor. On the basis of its distribution pattern the dolomite seems to have formed under shoal conditions, especially where it borders the shore of the Defiance positive element and along Peach Springs ridge. Oölitic limestone at the top of both major transgressive units is interpreted as reflecting the oscillatory conditions of sea level that provided wave and current agitation at times of maximum sea advance in shoal areas bordering the ridges. Aphanitic limestone, representing accumulations of lime mud, seems to be developed best in the uppermost, or Horseshoe Mesa, member, where, as the seas regressed, nearshore waters may have been isolated and certainly were very calm. Original textures and some structures are preserved in most limestones of the Redwall, and they give much evidence concerning oceanographic factors of the time. Generalizations have been developed concerning the character of the bottom, degrees of energy represented, depth, salinity, and other factors for various parts of the formation. Although these factors differed greatly with time and space, the general conclusions reached are that (1) depths were very shallow to moderate, (2) the sea floor was composed nearly entirely of lime mud and lime sand, which contained no terrigeneous material but with great crinoidal accumulations locally, (3) turbulence ranged from considerable to none, and (4) the sea was clear and warm and nowhere contained saline concentrations sufficient to form evaporites. Chert forming thin irregular beds, locally lenticular and nodular, occurs at two prinicpal positions in the stratigraphic section, and in each it alternates with thin beds of carbonate rock. Chert is prominent throughout the Thunder Springs Member and forms thin but definite zones near the top of the Mooney Falls Member. This chert is believed to have formed on the sea floor during early diagenesis, as evidenced by petrography, paleogeography, and faunal relations. Regional differences in the abundance and type of associated fossils, recorded on a series of 4-foot-square sample plots made throughout the Grand Canyon, suggest a probable relation between fossil distribution and genesis of the chert. The fauna of the Redwall is abundant and varied, but preservation in many places is poor, and numerous specimens can be collected only locally. The most common fossils are brachiopods, corals, foraminifers, and crinoids, but blastoids, gastropods, cephalopods, and pelecypods are not rare. Bryozoans are abundant in the chert of the Thunder Springs Member but uncommon elsewhere. Other organisms locally distributed but not common are algae, trilobites, fish, holothurians, and ostracodes. These groups have been studied by specialists and are the subject of Chapters V through XIII. Certain of the faunal groups, notably the corals and foraminifers, show some degree of vertical zoning and so have furnished important data on age and correlation. Among the corals, the zones of Dorlodotia inconstans and Michelinia expansa are especially significant because of their persistence from section to section across broad areas. The foraminiferal zones are broader and less sharply defined, but they represent a series of major changes in species from bottom to top of the formation. Age determination made on the basis of foraminifers and brachiopods indicate that the base of the Redwall is progressively younger as it passes from areas that were offshore eastward or northward toward the Defiance positive element; the top of the Redwall, in contrast, is shown to be progressively younger away from the positive element. Thus basal beds of Kinderhook age are recognized at Grand Wash, Quartermaster, and Meriwitica Canyons to the northwest, but the lowest strata are of Osage age at Bridge Canyon, Grandview, and other sections closer to the landmass. Likewise, units with fossils of middle Meramec age occur in western Grand Canyon, but, except in the one place discussed in the following paragraph, topmost beds farther east in Grand Canyon are of Osage age. South of Grand Canyon the youngest member of the Redwall (Horseshoe Mesa) has been removed by pre-Supai Formation erosion. Rocks still younger than the Horseshoe Mesa once may have covered the entire region, possibly representing a third sequence of transgression and regression. At Bright Angel trail in eastern Grand Canyon, for example, a unique unit at the top of the Redwall section contains fossils of Chester age and apparently represents a remnant of Late Mississippian rocks that survived as an inlier there.

Arizona↗