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Exploratory and spatial data analysis (EDA-SDA) for determining regional background levels and anomalies of potentially toxic elements in soils from Catorce-Matehuala, Mexico

The threshold between geochemical background and anomalies can be influenced by the methodology selected for its estimation. Environmental evaluations, particularly those conducted in mineralized areas, must consider this when trying to determinate the natural geochemical status of a study area, quantifying human impacts, or establishing soil restoration values for contaminated sites. Some methods in environmental geochemistry incorporate the premise that anomalies (natural or anthropogenic) and background data are characterized by their own probabilistic distributions. One of these methods uses exploratory data analysis (EDA) on regional geochemical data sets coupled with a geographic information system (GIS) to spatially understand the processes that influence the geochemical landscape in a technique that can be called a spatial data analysis (SDA). This EDA-SDA methodology was used to establish the regional background range from the area of Catorce-Matehuala in north-central Mexico. Probability plots of the data, particularly for those areas affected by human activities, show that the regional geochemical background population is composed of smaller subpopulations associated with factors such as soil type and parent material. This paper demonstrates that the EDA-SDA method offers more certainty in defining thresholds between geochemical background and anomaly than a numeric technique, making it a useful tool for regional geochemical landscape analysis and environmental geochemistry studies.

Applied Geochemistry↗

Evaluation of selected static methods used to estimate element mobility, acid-generating and acid-neutralizing potentials associated with geologically diverse mining wastes

A comparison study of selected static leaching and acid–base accounting (ABA) methods using a mineralogically diverse set of 12 modern-style, metal mine waste samples was undertaken to understand the relative performance of the various tests. To complement this study, in-depth mineralogical studies were conducted in order to elucidate the relationships between sample mineralogy, weathering features, and leachate and ABA characteristics. In part one of the study, splits of the samples were leached using six commonly used leaching tests including paste pH, the U.S. Geological Survey (USGS) Field Leach Test (FLT) (both 5-min and 18-h agitation), the U.S. Environmental Protection Agency (USEPA) Method 1312 SPLP (both leachate pH 4.2 and leachate pH 5.0), and the USEPA Method 1311 TCLP (leachate pH 4.9). Leachate geochemical trends were compared in order to assess differences, if any, produced by the various leaching procedures. Results showed that the FLT (5-min agitation) was just as effective as the 18-h leaching tests in revealing the leachate geochemical characteristics of the samples. Leaching results also showed that the TCLP leaching test produces inconsistent results when compared to results produced from the other leaching tests. In part two of the study, the ABA was determined on splits of the samples using both well-established traditional static testing methods and a relatively quick, simplified net acid–base accounting (NABA) procedure. Results showed that the traditional methods, while time consuming, provide the most in-depth data on both the acid generating, and acid neutralizing tendencies of the samples. However, the simplified NABA method provided a relatively fast, effective estimation of the net acid–base account of the samples. Overall, this study showed that while most of the well-established methods are useful and effective, the use of a simplified leaching test and the NABA acid–base accounting method provide investigators fast, quantitative tools that can be used to provide rapid, reliable information about the leachability of metals and other constituents of concern, and the acid-generating potential of metal mining waste.

Applied Geochemistry↗

Major and trace element composition of copiapite-group minerals and coexisting water from the Richmond mine, Iron Mountain, California

Copiapite-group minerals of the general formula AR 4 (SO 4 ) 6 (OH) 2 · n H 2 O, where A is predominantly Mg, Fe 2+ , or 0.67Al 3+ , R is predominantly Fe 3+ , and n is typically 20, are among several secondary hydrous Fe sulfates occurring in the inactive mine workings of the massive sulfide deposit at Iron Mountain, CA, a USEPA Superfund site that produces extremely acidic drainage. Samples of copiapite-group minerals, some with coexisting water, were collected from the Richmond mine. Approximately 200 mL of brownish pore water with a pH of −0.9 were extracted through centrifugation from a 10-L sample of moist copiapite-group minerals taken from pyritic muck piles. The pore water is extremely rich in ferric iron (Fe 3+ =149 g L −1 , Fe T =162 g L −1 ) and has a density of 1.52 g mL −1 . The composition of the pore water is interpreted in the context of published phase relations in the Fe 2 O 3 –SO 3 –H 2 O system and previous work on the chemistry of extremely acid mine waters and associated minerals in the Richmond mine. Two distinct members of the copiapite mineral group were identified in the samples with coexisting water: (1) abundant magnesiocopiapite consisting of platy crystals 10 to 50 μm and (2) minor aluminocopiapite present as smaller platy crystals that form spheroidal aggregates. The average composition ( n =5) of the magnesiocopiapite is (Mg 0.90 Fe 2+ 0.17 Zn 0.02 Cu 0.01 ) ∑1.10 (Fe 3+ 3.83 Al 0.09 ) ∑3.92 (SO 4 ) 6.00 (OH) 1.96 ·20H 2 O. Bulk compositions determined by digestion and wet-chemical analysis are consistent with the microanalytical results. These results suggest that magnesiocopiapite is the least soluble member of the copiapite group under the prevailing conditions. Micro-PIXE analysis indicates that the copiapite-group minerals in this sample sequester Zn (average 1420 ppm), with lesser amounts of Cu (average 270 ppm) and As (average 64 ppm).

Chemical Geology↗

On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

Chemical Geology↗

Zinc isotope and transition-element dynamics accompanying hydrozincite biomineralization in the Rio Naracauli, Sardinia, Italy

The Rio Naracauli in SW Sardinia drains part of the Ingurtosu Zn–Pb mining district, and contains extreme concentrations of dissolved Zn at near-neutral pH. In the upper reaches of the stream, pH, alkalinity and Zn concentrations are such that hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] precipitates in a biologically mediated process facilitated by a microalga ( Chlorella sp.) and a cyanobacterium ( Scytonema sp.). Values of δ 66 Zn in water and solid samples ranged from − 0.35‰ to + 0.5‰ relative to the JMC 3-0749-Lyon standard, and closely follow a mass-dependent fractionation line. Two composite samples of sphalerite, the primary ore mineral in the Ingurtosu deposits, had an average δ 66 Zn of + 0.15‰, similar to sphalerite measured elsewhere in hydrothermal mineral deposits. Zinc isotope measurements of the stream water and the hydrozincite forming in the stream show a consistent preference for the heavy isotope, 66 Zn, in the hydrozincite relative to 64 Zn. Synthetic hydrozincites produced without added bacteria have δ 66 Zn identical to the dissolved Zn, thus suggesting a biologically mediated mineralization process in Rio Naracauli. The average fractionation, Δ hdz-water , is 0.35‰, the magnitude of which is consistent with other studies, and suggests an extracellular mechanism of the biomineralization process. Zinc concentration and dissolved δ 66 Zn steadily decrease in the reach of the stream where the biomineralization occurs. The biomineralization process also leads to the sequestration of Pb, Cu and Ni in the hydrozincite lattice, and the coeval precipitation of an amorphous CdCO 3 solid, prompting the suggestion that if optimized, the biomineralization process might represent a feasible passive remediation strategy for streams with high Zn and other metals, and with near-neutral pH.

Sardinia↗

Mercury and other element exposure in tree swallows nesting at low pH and neutral pH lakes in northern Wisconsin USA

The primary objective of this study was to determine whether tree swallows ( Tachycineta bicolor ) demonstrate similar responses to lake pH and mercury (Hg) contamination in northern Wisconsin as do common loons ( Gavia immer ). Similar to common loons, Hg concentrations in the blood of tree swallow nestlings were higher, Hg concentrations in eggs tended to be higher, and egg size tended to be smaller at low (<6.2) pH lakes. In contrast to common loons, tree swallow nestling production was not lower at low pH lakes. Based on modeling associations, Hg concentrations in tree swallow eggs and nestling blood can be used to predict Hg concentrations in common loons without the invasive or destructive sampling of loons. Mean concentrations of cadmium, manganese, and mercury in nestling livers were higher at low pH lakes than neutral pH lakes. Concentrations of cadmium, chromium, mercury, selenium, and zinc were not at toxic levels.

Wisconsin↗

Temperature-dependent variations in mineralogy, major element chemistry and the stable isotopes of boron, lithium and chlorine resulting from hydration of rhyolite glass: Constraints from hydrothermal experiments at 150 to 350°C and 25 MPa

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m ) to hydroxyl (OH − ) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes.

Geochimica et Cosmochimica Acta↗

Geochemical factors controlling dissolved elemental mercury and methylmercury formation in Alaskan wetlands of varying trophic status

Transformations of aqueous inorganic divalent mercury (Hg(II)i) to volatile dissolved gaseous mercury (Hg(0)(aq)) and toxic methylmercury (MeHg) governs mercury bioavailability and fate in northern ecosystems. This study quantified concentrations of aqueous mercury species (Hg(II)i, Hg(0)(aq), MeHg) and relevant geochemical constituents in pore waters of eight Alaskan wetlands that differ in trophic status (i.e., bog-to-fen gradient) to gain insight on processes controlling dark Hg(II)i reduction and Hg(II)i methylation. Regardless of wetland trophic status, positive correlations were observed between pore water Hg(II)i and dissolved organic carbon (DOC) concentrations. The concentration ratio of Hg(0)(aq) to Hg(II)i exhibited an inverse relationship to Hg(II)i concentration. A ubiquitous pathway for Hg(0)(aq) formation was not identified based on geochemical data, but we surmise that dissolved organic matter (DOM) influences mercury retention in wetland pore waters by complexing Hg(II)i and decreasing the concentration of volatile Hg(0)(aq) relative to Hg(II)i. There was no evidence of Hg(0)(aq) abundance directly limiting mercury methylation. The concentration of MeHg relative to Hg(II)i was greatest in wetlands of intermediate trophic status, and geochemical data suggest mercury methylation pathways vary between wetlands. Our insights on geochemical factors influencing aqueous mercury speciation should be considered in context of the long-term fate of mercury in northern wetlands.

Environmental Science & Technology↗