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USGS2001

Irrigation drainage studies of the Angostura Reclamation Unit and the Belle Fourche Reclamation Project, western South Dakota: Results of 1994 sampling and comparisons with 1988 data

The U.S. Department of the Interior started the National Irrigation Water Quality Program in 1985 to identify the nature and extent of irrigation-induced water-quality problems that might exist in the western U.S. The Angostura Reclamation Unit (ARU) and Belle Fourche Reclamation Project (BFRP) in western South Dakota were included as part of this program. The ARU and BFRP reconnaissance studies were initiated in 1988, during below-normal streamflow conditions in both study areas. Surface water, bottom sediment, and fish were resampled in 1994 at selected sites in both study areas during generally near-normal streamflow conditions to compare with 1988 study results. Concentrations of major ions in water for both the ARU and BFRP study areas are high relative to national baseline levels. Major-ion concentrations for both areas generally are lower for 1994 than for 1988, when low-flow conditions prevailed, but ionic proportions are similar between years. For ARU, dissolved-solids concentrations probably increase slightly downstream from Angostura Reservoir; however, the available data sets are insufficient to confidently discern effects of ARU operations on dissolved-solids loading. For BFRP, dissolved-solids concentrations are slightly higher at sites that are affected by irrigation drainage; again, however, the data are inconclusive to determine whether BFRP operations increase dissolved-solids loading. Most trace-element concentrations in water samples for both study areas are similar between 1988 and 1994, and do not show strong relations with discharge. ARU operations probably are not contributing discernible additional loads of trace elements to the Cheyenne River. For BFRP, concentrations of some trace elements are slightly higher at sites downstream from irrigation operations than at a site upstream from irrigation operations. BFRP operations might contribute to trace-element concentrations in the Belle Fourche River, but available data are insufficient to quantify increases. For both study areas, concentrations of several trace elements occasionally exceed National Irrigation Water Quality Program guidelines. Selenium routinely occurs in concentrations that could be problematic at sites upstream and downstream from both study areas. Elevated selenium concentrations at sites upstream from irrigation operations indicate that naturally occurring selenium concentrations are relatively high in and near the study areas. While ARU operations probably do not contribute discernible additional loads of selenium to the Cheyenne River, BFRP operations might contribute additional selenium loads to the Belle Fourche River. Concentrations of most trace elements in bottom sediment, except arsenic and selenium, are similar to typical concentrations for western U.S. soils for both study areas. Bottom-sediment arsenic and selenium (1988) concentrations in both study areas can reach levels that might be of concern; however, there is insufficient information to determine whether irrigation operations contribute to these elevated concentrations. Concentrations of most trace elements in fish in both study areas are less than values known to adversely affect fish or birds, although there are occasional exceedances of established criteria. However, selenium concentrations in fish samples routinely are within the National Irrigation Water Quality Program level of concern, and also commonly exceed the dietary guideline for avian consumers for both study areas. Selenium concentrations in fish samples generally are higher at sites downstream from irrigation operations. For BFRP, arsenic and mercury concentrations are elevated in fish samples from site B-18, which is influenced by mine tailings.

South Dakota↗

USGS2002

Hydrogeology and water quality of the Upper Three Runs aquifer in the vicinity of the Gibson Road Landfill, Fort Gordon, Georgia, June-November 1999

Fort Gordon military installation, a U.S. Department of the Army facility, is located in east-central Georgia southwest of Augusta. The military base operates a three-phase unlined landfill—Gibson Road Landfill— to store a variety of wastes. Phases I and II stored only household wastes, and these phases were discontinued during the mid–1990s. Fort Gordon currently (1999) operates Phase III of the landfill that stores only construction and demolition debris. Water-quality monitoring detected selected trace elements and organic compounds exceeding the maximum contaminant levels of the U.S. Environmental Protection Agency, National Primary Drinking Water Standards. The selected trace elements and organic compounds detected showed that contamination of ground water had occurred in the vicinity of the landfill. In 1999, the U.S. Geological Survey, in cooperation with the Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, Georgia, began an assessment of the hydrogeology and water quality in shallow ground water in the vicinity of the Gibson Road Landfill to delineate the extent of a ground-water contamination plume in the vicinity of the landfill. Hydrogeologic units in the Augusta area include the Upper Three Runs aquifer, the Gordon aquifer, the Millers Pond aquifer, and the Dublin aquifer. Only the shallowest aquifer, Upper Three Runs, was penetrated during this study. The Upper Three Runs aquifer is composed of sediments of the Barnwell Group. Mostly, these sediments are highly permeable fine to medium, well-sorted sand with lenses of clay. Ground-water flow is from northwest to southeast and generally was unaffected by seasonal variation during the period of study (June–November 1999). Water-table altitudes in the landfill area for the study period ranged from 394 feet (ft) to 445 ft above sea level. Ground-water samples analyzed for organic compounds and selected trace elements by a U. S. Environmental Protection Agency (USEPA) approved statistical test revealed that increases in contaminant concentrations above the detection limits had occurred during March and September 1999 in five wells—one of which is located upgradient. These organic compounds, respective increases in concentration, and the wells in which they were detected are: methylene chloride—wells 28AA29 (24 parts per billion [ppb] and 46 ppb), 28AA30 (86 ppb and 130 ppb), and 28AA31 (240 ppb and 140 ppb); 1,1-dichloroethene—well 28AA31 (10 ppb and 5.7 ppb); 1,1-dichloroethane— wells 28AA30 (81 ppb and 140 ppb) and 28AA31 (200 ppb and 130 ppb); and 1,1,1-trichloroethane—well 28AA31 (61 ppb and 37 ppb). Although in some wells the concentration decreased from March to September, the median concentrations were still higher in certain groups. Trace element compounds, their respective increases in concentration, and the wells in which they were detected are: chromium—well 28AA30 (1,190 ppb), vanadium—well 28AA30 (104 ppb); barium—wells 28AA27 (42.2 ppb) and 28AA32 (140 ppb), and beryllium—well 28AA30 (6.3 ppb). These increases occurred in September, with the exception of chromium in well 28AA30, which occurred in March. Although a statistical test indicated increases in contaminant concentrations had occurred, water from wells 28AA27, 28AA30, 28AA31, and 28AA32 had a decrease in contaminant concentrations from February 1998 to September 1999. U.S. Environmental Protection Agency, National Primary Drinking Water Regulations Maximum Contaminant Levels (PMCLs), formerly (MCLs) were exceeded in water from four wells for organic compounds and in five wells by selected trace elements during the February 1998, March 1999, and September 1999 sampling periods. The concentrations for the following organic compounds and the associated wells are: methylene chloride (PMCL is 5 ppb)—wells 28AA27 (February, 37 ppb; March, 24 ppb; and September, 9.6 ppb), 28AA29 (February, 20 ppb; March, 24 ppb; and September, 46 ppb), 28AA30 (February, 50 ppb; March, 86 ppb; and September, 130 ppb), and 28AA31 (February, 330 ppb; March 240 ppb; and September, 140 ppb); vinyl chloride (PMCL is 2 ppb)—well 28AA29 (March, 3.6 ppb; and September, 4.4 ppb); 1,1-dichloroethene (PMCL is 7 ppb)—wells 28AA30 (March 10 ppb; and September, 17 ppb) and 28AA31 (February, 13 ppb; and March, 10 ppb); and 1,1,2-trichloroethane (PMCL is 5 ppb)—well 28AA30 (March, 33 ppb). Contaminant concentrations decreased in well 28AA31 from March to September 1999; however, concentrations still exceeded the PMCL. The concentrations for the following selected trace elements exceeding PMCL and the associated wells during the sampling periods February 1998, March 1999, and September 1999 are: mercury (PMCL is 2 ppb)—well 28AA24 (September, 2.82 ppb), well 28AA25 (February, 3.1 ppb; March, 2.11 ppb; and September, 2.28 ppb), and well 28AA30 (September, 2.82 ppb); arsenic (PMCL is 50 ppb)—well 28AA30 (February, 90 ppb; and September, 114 ppb); thallium (PMCL is 2 ppb)—wells 28AA27 (March, 2.08 ppb) and 28AA29 (February, 2.56); barium (PMCL is 2,000 ppb)—well 28AA30 (March, 4,490 ppb); chromium (PMCL is 30 ppb)—well 28AA30 (February, 630 ppb; and March, 1,190 ppb); and beryllium (PMCL is 4 ppb)—well 28AA30 (September, 6.3 ppb). Water from seven wells, three of which are upgradient of the landfill, contained organic compounds and/or selected trace elements exceeding PMCLs during the period February 1998 to September 1999 according to private consultants. Contaminants present in upgradient wells most likely were caused by chemical dispersion, leachate migration, incorrectly defined landfill area, or natural ground-water flow beneath the landfill.

Georgia↗

USGS1999

Cobalt-rich ferromanganese crusts in the Pacific

Co-rich Fe-Mn crusts occur throughout the Pacific on seamounts, ridges, and plateaus where currents have kept the rocks swept clean of sediments at least intermittently for millions of years. Crusts precipitate out of cold ambient sea water onto hard-rock substrates forming pavements up to 250 mm thick. Crusts are important as a potential resource for Co, Ni, Pt, Mn, Tl, Te, and other metals, as well as for the paleoclimate signals stored in their stratigraphic layers. Crusts form at water depths of about 400 to 4000 m, with the thickest and most Co-rich crusts occurring at depths of about 800 to 2500 m, which may vary on a regional scale. Gravity processes, sediment cover, submerged and emergent reefs, and currents control the distribution and thickness of crusts on seamounts. Crusts occur on a variety of substrate rocks that generally decrease in the order, breccia, basalt, phosphorite, limestone, hyaloclastite, and mudstone. Because of this wide variety of substrate types, crusts are difficult to distinguish from the substrate using remotely sensed data, such as geophysical measurements, but are generally weaker and lighter-weight than the substrate. Crusts can be distinguished from the substrates, however, by their much higher gamma radiation levels. The mean dry bulk density of crusts is 1.3 g/cm3, the mean porosity is 60%, and the mean surface area is extremely high, 300 m2/g. Crusts generally grow at rates of 1 to 10 mm/Ma. Crust surfaces are botryoidal, which may be modified to a variety of forms by current erosion. In cross-section, crusts are generally layered, with individual layers displaying massive, botryoidal, laminated, columnar, or mottled textures. Characteristic layering is persistent regionally in the Pacific. Crusts are composed of ferruginous vernadite (δ-MnO2) and X-ray amorphous Fe oxyhydroxide, with moderate amounts of carbonate fluorapatite (CFA) in thick crusts and minor amounts of quartz and feldspar in most crusts. Elements most commonly associated with the vernadite phase include Mn, Co, Ni, Cd, and Mo, whereas those most commonly associated with Fe oxyhydroxide are Fe and As. Detrital phases are represented by Si, Al, K, Ti, Cr, Mg, Fe, and Na; the CFA phase by Ca, P, Sr, Y, and CO2; and a residual biogenic phase by Ba, Sr, Ce, Cu, V, Ca, and Mg. Crusts contain Co contents up to about 2.3%, Ni to 1%, and Pt to 3 ppm, with mean Fe/Mn ratios of 0.6 to 1.3. Fe/Mn decreases, whereas Co, Ni, Ti, and Pt increase in central Pacific crusts and Fe/Mn, Si, and Al increase in continental margin crusts and in crusts with proximity to west Pacific volcanic arcs. Vernadite and CFA-related elements decrease, whereas Fe, Cu, and detrital-related elements increase with increasing water depth of crust occurrence. Cobalt, Ce, Tl, and maybe also Ti, Pb, and Pt are strongly concentrated in crusts over other metals because of oxidation reactions. Total rare earth elements (REEs) commonly vary between 0.1% and 0.3% and are derived from sea water along with other hydrogenetic elements, Co, Mn, Ni, etc. Platinum, Rh, Ir, and some Ru in crusts are also derived from sea water, whereas Pd and the remainder of the Ru derive from detrital minerals. The older parts of thick crusts were phosphatized during at least two global phosphogenic events during the Tertiary, which mobilized and redistributed elements in those parts of the crusts. 240Silicon, Fe, Al, Th, Ti, Co, Mn, Pb, and U are commonly depleted, whereas Ni, Cu, Zn, Y, REEs, Sr, and Pt are commonly enriched in phosphatized layers compared to younger nonphosphatized layers. The dominant controls on the concentration of elements in crusts include the concentration of metals in sea water and their ratios, colloid surface charge, types of complexing agents, surface area, and growth rates. Crusts act as closed systems with regard to the isotopic ratios of Be, Nd, Pb, Hf, Os, and U-series, which in part have been used to date crusts and in part used as isotopic tracers of paleoceanographic and paleoclimatic conditions. Those tracers are especially useful in delineating temporal changes in deep-ocean circulation. Research and development on the technology of mining crusts are only in their infancy. Detailed maps of crust deposits and a better understanding of small-scale seamount topography are required to design the most appropriate mining equipment.

Book chapter↗

USGS1974

Energy dispersive spectrometry for quantitative mineralogical analyses: An ancillary system on an electron microphobe

Investigation of the Li-drifted Si-semiconductor X-ray detector for quantitative elemental analysis of some common rock-forming minerals shows that amounts of certain major elements having K spectra in the energy range of about 1.74 (Si) to 8.64 (Zn) kiloelectronvolts may be accurately determined, if spectral interferences are absent. Elements in major concentrations between 0.5 and 1.00 percent may be analyzed quantitatively without corrections of K spectra X-ray intensities when reference standards of similar composition are used and significant K spectra interferences between two adjacent elements are absent. Elemental concentrations less than about 0.5 weight percent cannot be precisely determined from raw X-ray intensity data owing to high and variable spectral background. Data show that spectral background corrections are feasible because spectral background is a linear function for the light-element oxides and silicates. Simultaneous quantitative elemental analysis, with both the energy dispersive spectrometer and the conventional wavelength dispersive spectrometers on the electron microprobe, is feasible.

Journal of Research of the U.S. Geological Survey↗

USGS2014

The geology and geochemistry of Isla Floreana, Galápagos: A different type of late-stage ocean island volcanism

Isla Floreana, the southernmost volcano in the Galápagos Archipelago, has erupted a diverse suite of alkaline basalts continually since 1.5 Ma. Because these basalts have different compositions than xenoliths and older lavas from the deep submarine sector of the volcano, Floreana is interpreted as being in a rejuvenescent or late-stage phase of volcanism. Most lavas contain xenoliths, or their disaggregated remains. The xenolithic debris and large ranges in composition, including during single eruptions, indicate that the magmas do not reside in crustal magma chambers, unlike magmas in the western Galápagos. Floreana lavas have distinctive trace element compositions that are rich in fluid-immobile elements (e.g., Ta, Nb, Th, Zr) and even richer in fluid-mobile elements (e.g., Ba, Sr, Pb). Rare earth element (REE) patterns are light REE-enriched and distinctively concave-up. Neodymium isotopic ratios are comparable to those from Fernandina, at the core of the Galápagos plume, but Floreana has the most radiogenic Sr and Pb isotopic ratios in the archipelago. These trace element patterns and isotopic ratios are attributed to a mixed source originating within the Galápagos plume, which includes depleted upper mantle, plume material rich in TITAN elements (Ti, Ta, Nb), and recycled oceanic crust that has undergone partial dehydration in an ancient subduction zone. Because Floreana lies at the periphery of the Galápagos plume, melting occurs mostly in the spinel zone, and enriched components dominate; the Floreana recycled mantle component influence is detectable in volcanoes along the entire southern periphery of the archipelago as well. Floreana is the only Galápagos volcano known to have undergone late-stage volcanism. Here, however, the secondary stage activity is more compositionally enriched than the shield-building phase, in contrast to what is observed in Hawai‘i, suggesting that the mechanism driving late-stage volcanism may vary among ocean island provinces.

Galápagos, Isla Floreana↗

USGS1992

Compositional gradients in large reservoirs of silicic magma as evidenced by ignimbrites versus Taylor Creek Rhyolite lava domes

The Taylor Creek Rhyolite of southwest New Mexico consists of 20 lava domes and flows that were emplaced during a period of a few thousand years or less in late Oligocene time. Including genetically associated pyroclastic deposits, which are about as voluminous as the lava domes and flows, the Taylor Creek Rhyolite represents roughly 100 km3 of magma erupted from vents distributed throughout an area of several hundred square kilometers. Major-element composition is metaluminous to weakly peraluminous high-silica rhyolite and is nearly constant throughout the lava field. The magma reservoir for the Taylor Creek Rhyolite was vertically zoned in trace elements, 87Sr/86Sr, and phenocryst abundance and size. Mean trace-element concentrations, ranges in concentrations, and element-pair correlations are similar to many subalkaline silicic ignimbrites. However, the polarity of the zonation was opposite that in reservoirs for ignimbrites, for most constituents. For example, compared to the Bishop Tuff, only 87Sr/86Sr and Sc increased upward in both reservoirs. Quite likely, a dominant but nonerupted volume of the magma reservoir for the Taylor Creek Rhyolite was zoned like that for the Bishop Tuff, whereas an erupted, few-hundred-meter-thick cap on the magma body was variably contaminated by roof rocks whose contribution to this part of the magma system moderated relatively extreme trace-element concentrations of uncontaminated Taylor Creek Rhyolite but did not change the sense of correlation for most element pairs. The contaminant probably was a Precambrian rock of broadly granitic composition and with very high 87Sr/86Sr. Although examples apparently are not yet reported in the literature, evidence for a similar thin contaminated cap on reservoirs for large-volume silicic ignimbrites may exist in the bottom few meters of ignimbrites or perhaps only in the pumice fallout that normally immediately precedes ignimbrite emplacement. 87Sr/86Sr in sanidine phenocrysts of the Taylor Creek Rhyolite is higher than that of their host whole rocks. Covariation of this isotope ratio with sanidine abundance and size indicates positive correlations for all three features with decreasing distance to the roof of the magma reservoir. The sanidine probably is more radiogenic than host whole rock because growing phenocrysts partly incorporated Sr from the first partial melt of roof rocks, which contained the highly radiogenic Sr of Precambrian biotite ?? hornblende, whereas diffusion was too slow for sanidine to incorporate much of the Sr from subsequently produced less radiogenic partial melt of roof rocks, before eruption quenched the magma system. Disequilibrium between feldspar phenocrysts and host groundmass is fairly common for ignimbrites, and a process of contamination similar to that for the Taylor Creek Rhyolite may help explain some of these situations. ?? 1992 Springer-Verlag.

Contributions to Mineralogy and Petrology↗

USGS1984

Petrochemistry, age and isotopic composition of alkali basalts from Ponape Island, Western Pacific

Eleven analyzed lava samples from Ponape Island are alkali olivine basalt, basanite and basanitoid. Most lavas are aphyric or sparsely phyric (< 10% phenocrysts) and have phenocrysts of olivine (Fo77-80), clinopyroxene and titanomagnetite, and microphenocrysts of plagioclase (An53-68) in a fine-grained groundmass of olivine, clinopyroxene, plagioclase, opaques, potassic oligoclase, ?? nepheline and accessary phases. Oxygen isotope and Fe2O3 FeO data suggest that most samples are fresh, although H2O contents are high. Xenoliths of chromite-bearing harzburgites and dunites, both with cumulate textures occur in one locality. Major- and trace-element concentrations are similar to other oceanic volcanic islands. Most major elements and compatible trace elements vary systematically with respect to the Mg number [ 100Mg (Mg + Fe2+)]. In contrast, the incompatible trace elements do not correlate with the Mg number, but do covary with other incompatible elements. Simple closed-system shallow fractionation cannot be invoked to explain the observed chemical variation in the lavas. Derivation of the fractionated lavas (Mg number = 66-48) probably involved polybaric crystal fractionation from a high-Mg-number parental liquid. In addition, variable-source concentration of a trace-element-rich minor phase is postulated. However, the mantle was homogeneous with respect to the ratio of 87Sr 86Sr. New KAr age data are not consistent with the hypothesis that Ponape and the Caroline Ridge represent a simple "hot spot". ?? 1984.

Chemical Geology↗

USGS1985

Geochemistry and petrogenesis of lamproites, late cretaceous age, Woodson County, Kansas, U.S.A.

Lamproite sills and their associated sedimentary and contact metamorphic rocks from Woodson County, Kansas have been analyzed for major elements, selected trace elements, and strontium isotopic composition. These lamproites, like lamproites elsewhere, are alkalic (molecular K 2 O + Na 2 O Al 2 O 3 = 1.6–2.6 "> K 2 O + Na 2 OAl 2 O 3 = 1.6–2.6 ), are ultrapotassic ( K 2 O Na 2 O = 9.6–150) "> (K 2 ONa 2 O= 9.6–150) , are enriched in incompatible elements (LREE or light rare-earth elements, Ba, Th, Hf, Ta, Sr, Rb), and have moderate to high initial strontium isotopic compositions (0.7042 and 0.7102). The silica-saturated magma (olivine-hypersthene normative) of the Silver City lamproite could have formed by about 2 percent melting of a phlogopite-garnet lherzolite under high H 2 O CO 2 "> H 2 OCO 2 ratios in which the Iherzolite was enriched before melting in the incompatible elements by metasomatism. The Rose Dome lamproite probably formed in a similar fashion although the extreme alteration due to addition of carbonate presumably from the underlying limestone makes its origin less certain. Significant fractional crystallization of phases that occur as phenocrysts (diopside, olivine, K-richterite, and phlogopite) in the Silver City magma and that concentrate Co, Cr, and Sc are precluded as the magma moved from the source toward the surface due to the high abundances of Co, Cr, and Sc in the magma similar to that predicted by direct melting of the metasomatized Iherzolite. Ba and, to a lesser extent, K and Rb and have been transported from the intrusions at shallow depth into the surrounding contact metamorphic zone. The Silver City lamproite has vertical fractionation of some elements due either to volatile transport or to variations in the abundance of phenocrysts relative to groundmass most probably due to flow differentiation although multiple injection or fractional crystallization cannot be conclusively rejected.

Geochimica et Cosmochimica Acta↗

USGS1981

Regional geochemical studies in the Patagonia Mountains, Santa Cruz County, Arizona

The Patagonia Mountains in southern Arizona contain the deeply buried porphyry copper system at Red Mountain as well as a number of other base- and precious-metal mines and prospects. The range contains complex Basin and Range geology with units ranging in age from Precambrian to Holocene. Rock types present include igneous intrusive and extrusive units as well as sedimentary and metamorphic units, most of which have been tectonically disturbed. A total of 264 stream-sediment samples were collected and analyzed for 32 elements. Geochemical maps for Sb, Ag, Pb, Te, B, Mn, Au, Zn, Cu (total), Cu (cold-extractable), and Mo, as well as for Cu (cold-extractable)/Cu (total) and Fe/Mn, are presented. Anomaly patterns for these elements generally occur over the Red Mountain deposit and (or) along a north-northwest trend parallel to the major Harshaw Creek Fault. Much of the entire area sampled contains widespread anomalies for Pb, Te, and Cu; the other elements are only locally anomalous. Various plots of ratios of Cu (cold-extractable) to Cu (total) did not produce any new information not readily apparent on either one of the two copper maps. A plot of ratios of Fe to Mn delineated many areas of pyrite mineralization. Several of these areas may represent the pyritic halos around deeply buried porphyry copper systems. The best ore guide for the Red Mountain porphyry system is the coincidence of positive anomalies of Mo, Pb, and Te and a negative anomaly of Mn. Other areas with anomalies of the same suite of elements are present within the Patagonia Mountains. It is concluded that geochemical sampling, even in a highly contaminated area, can be useful in delineating major geologic features, such as porphyry copper belts and major faults. Multielement geochemical surveys on a regional scale can effectively locate large, deeply buried, zoned mineral systems such as that at Red Mountain. Plots of element ratios, where adequately understood, can provide geochemical information not readily discernible from plots of single elements alone.

Arizona↗

USGS1992

Decomposition techniques

Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed.

Journal of Geochemical Exploration↗

USGS2018

Environmental characteristics and utilization potential of metallurgical slag

Slag, an abundant byproduct from the pyrometallurgical processing of ores, can be an environmental liability or a valuable resource. The most common environmental impact of slag is from the leaching of potentially toxic elements, acidity, or alkalinity that may impact nearby soils and surface water and groundwater. Factors that influence its environmental behavior include physical characteristics, such as grain size and porosity, chemical composition with some slag being enriched in certain elements, the mineralogy and partitioning of elements in more or less reactive phases, water-slag interactions, and site conditions. Many of these same factors also influence its resource potential. For example, crystalline ferrous slag is most commonly used as construction aggregate, whereas glassy (i.e., granulated) slag is used in cement. Also, the calcium minerals found in ferrous slag result in useful applications in water treatment. In contrast, the high trace-element content of some base-metal slags makes the slags economically attractive for extraction of residual elements. An evaluation tool is used to help categorize a particular slag as an environmental hazard or valuable byproduct. Results for one type of slag, legacy steelmaking slag from the Chicago area in the USA, suggest the material has potential to be used for treating phosphate-rich or acidic waters; however, the pH and trace-element content of resulting solutions may warrant further examination.

Book chapter↗

USGS2005

Statistical characterization of a large geochemical database and effect of sample size

The authors investigated statistical distributions for concentrations of chemical elements from the National Geochemical Survey (NGS) database of the U.S. Geological Survey. At the time of this study, the NGS data set encompasses 48,544 stream sediment and soil samples from the conterminous United States analyzed by ICP-AES following a 4-acid near-total digestion. This report includes 27 elements: Al, Ca, Fe, K, Mg, Na, P, Ti, Ba, Ce, Co, Cr, Cu, Ga, La, Li, Mn, Nb, Nd, Ni, Pb, Sc, Sr, Th, V, Y and Zn. The goal and challenge for the statistical overview was to delineate chemical distributions in a complex, heterogeneous data set spanning a large geographic range (the conterminous United States), and many different geological provinces and rock types. After declustering to create a uniform spatial sample distribution with 16,511 samples, histograms and quantile-quantile (Q-Q) plots were employed to delineate subpopulations that have coherent chemical and mineral affinities. Probability groupings are discerned by changes in slope (kinks) on the plots. Major rock-forming elements, e.g., Al, Ca, K and Na, tend to display linear segments on normal Q-Q plots. These segments can commonly be linked to petrologic or mineralogical associations. For example, linear segments on K and Na plots reflect dilution of clay minerals by quartz sand (low in K and Na). Minor and trace element relationships are best displayed on lognormal Q-Q plots. These sensitively reflect discrete relationships in subpopulations within the wide range of the data. For example, small but distinctly log-linear subpopulations for Pb, Cu, Zn and Ag are interpreted to represent ore-grade enrichment of naturally occurring minerals such as sulfides. None of the 27 chemical elements could pass the test for either normal or lognormal distribution on the declustered data set. Part of the reasons relate to the presence of mixtures of subpopulations and outliers. Random samples of the data set with successively smaller numbers of data points showed that few elements passed standard statistical tests for normality or log-normality until sample size decreased to a few hundred data points. Large sample size enhances the power of statistical tests, and leads to rejection of most statistical hypotheses for real data sets. For large sample sizes (e.g., n > 1000), graphical methods such as histogram, stem-and-leaf, and probability plots are recommended for rough judgement of probability distribution if needed. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2015

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↗

USGS2007

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↗

USGS2006

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↗

USGS2008

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↗

USGS2010

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↗

USGS2014

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↗