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Hydration state and rheologic stratification of the lithospheric mantle beneath the North Anatolian Fault, Turkey

We present constraints on the hydration state and rheology of the lithospheric mantle beneath the North Anatolian fault zone (NAFZ). Peridotite xenoliths from the Biyikali and Çorlu volcanic centers record deformational microstructures consistent with shearing in a lithosphere-scale transcurrent fault system. Analysis by Fourier transform infrared spectroscopy indicates that nominally anhydrous phases retain some OH − , but bulk rock concentrations are generally restricted to <50 ppm H 2 O by weight. From the rock microstructure, we determined differential stress magnitude and active deformation mechanism(s); combined with estimates of hydration state, we constrained the rheology. Recrystallized grain size piezometry shows that the mantle beneath the NAFZ sustained differential stresses of 10–20 MPa, largely independent of depth. The dominant deformation mechanism(s) change with depth; xenoliths extracted from shallower depths record evidence for grain size-sensitive creep possibly in the presence of melt. At intermediate depths, both dislocation creep and grain size-sensitive mechanisms were active, and we did not observe evidence for deformation in the presence of melt. The deepest samples were dominated by dislocation creep. The strong temperature sensitivity of creep mechanisms, combined with the low variability in differential stress, contributes to a stratified viscosity profile ranging from 10 18 Pa s for the deepest samples to >10 22 Pa s at shallower depths (assuming a melt-free rheology). Although difficult to quantify from the rock record, melt likely reduced the viscosity of the shallow lithospheric mantle. Vertical stratification in viscosity beneath the NAFZ, the result of melt-present deformation and/or transitions in the dominant deformation mechanism, has important consequences for the seismic cycle of strike-slip fault systems.

North Anatolian fault zone

Vegetation loss following vertical drowning of Mississippi River deltaic wetlands leads to faster microbial decomposition and decreases in soil carbon

Wetland ecosystems hold nearly a third of the global soil carbon pool, but as wetlands rapidly disappear the fate of this stored soil carbon is unclear. The aim of this study was to quantify and then link potential rates of microbial decomposition after vertical drowning of vegetated tidal marshes in coastal Louisiana to known drivers of anaerobic decomposition altered by vegetation loss. Profiles of potential CH 4 and CO 2 production (surface to 60 cm deep) were measured during anaerobic incubations, organic matter chemistry was assessed with infrared spectroscopy, and soil porewater nutrients and redox potentials were measured in the field along a chronosequence of wetland loss. After vertical drowning, pond soils had lower redox potentials, higher pH values, lower soil carbon and nitrogen concentrations, lower lignin: polysaccharide ratios, more NH 4 + and PO 4 3− , and higher rates of potential CO 2 release than vegetated marsh soils. Potential CH 4 production was similar in vegetated marshes and open water ponds, with depth-dependent decreases in CH 4 production as soil carbon concentrations increased. In these anoxic soils, vegetation loss exerts a primary control on decomposition rates because flooding drives sustained increases in porewater nutrient availability (NH 4 + and PO 4 3 , dissolved organic carbon) and decreases in redox potential (from −150 to −500 mV) that lead to higher potential CO 2 fluxes within a few years. Without new carbon inputs following wetland loss, the sustained decomposition in open water ponds may lead to losses of stored soil carbon and could influence global carbon budgets.

Louisiana

Light absorbing particles deposited to snow cover across the Upper Colorado River Basin, Colorado Rocky Mountains, 2013-16: Interannual variations from multiple natural and anthropogenic sources

Atmospheric particulate matter (PM) as light-absorbing particles (LAPs) deposited to snow cover can result in early onset and rapid snow melting, challenging management of downstream water resources. We identified LAPs in 38 snow samples (water years 2013–2016) from the mountainous Upper Colorado River basin by comparing among laboratory-measured spectral reflectance, chemical, physical, and magnetic properties. Dust sample reflectance, averaged over the wavelength range of 0.35–2.50 μm, varied by a factor of 1.9 (range, 0.2300–0.4444) and was suppressed mainly by three components: (a) carbonaceous matter measured as total organic carbon (1.6–22.5 wt. %) including inferred black carbon, natural organic matter, and carbon-based synthetic, black road-tire-wear particles, (b) dark rock and mineral particles, indicated by amounts of magnetite (0.11–0.37 wt. %) as their proxy, and (c) ferric oxide minerals identified by reflectance spectroscopy and magnetic properties. Fundamental compositional differences were associated with different iron oxide groups defined by dominant hematite, goethite, or magnetite. These differences in iron oxide mineralogy are attributed to temporally varying source-area contributions implying strong interannual changes in regional source behavior, dust-storm frequency, and (or) transport tracks. Observations of dust-storm activity in the western U.S. and particle-size averages for all samples (median, 25 μm) indicated that regional dust from deserts dominated mineral-dust masses. Fugitive contaminants, nevertheless, contributed important amounts of LAPs from many types of anthropogenic sources.

Colorado

Corundum discovered by SuperCam and the Perseverance rover at Jezero crater, Mars

Mars is primarily composed of mafic mineral assemblages and their alteration products, but small, scattered rocks strewn across the landscape offer clues to greater petrological diversity. While traversing the Jezero crater rim, the Perseverance rover encountered several plagioclase-rich light-toned float rocks. SuperCam identified the distinctive signature of corundum (α-Al 2 O 3 ) in these rocks using time-resolved luminescence spectroscopy. Two strong peaks (692.7 and 694.1 nm) with millisecond lifetimes, and additional supporting lines, are consistent with Cr 3+ substitution for Al 3+ in corundum. Corundum forms in Al-rich, Si-depleted environments through magmatic or metamorphic processes. Given the rocks' small size, association with plagioclase, and location on the crater rim, we interpret the most plausible formation scenario to be impact induced metamorphism at the interface of a felsic and a mafic/ultramafic member with the likely action of fluids at some stage, although other possibilities are not excluded.

Geophysical Research Letters

Relation of nickel concentrations in tree rings to groundwater contamination

Increment cores were collected from trees growing at two sites where groundwater is contaminated by nickel. Proton-induced X ray emission spectroscopy was used to determine the nickel concentrations in selected individual rings and in parts of individual rings. Ring nickel concentrations were interpreted on the basis of recent concentrations of nickel in aquifers, historical information about site use activities, and model simulations of groundwater flow. Nickel concentrations in rings increased during years of site use but not in trees outside the contaminated aquifers. Consequently, it was concluded that trees may preserve in their rings an annual record of nickel contamination in groundwater. Tulip trees and oaks contained higher concentrations of nickel than did sassafras, sweet gum, or black cherry. No evidence was found that nickel accumulates consistently within parts of individual rings or that nickel is translocated across ring boundaries.

Water Resources Research

Water-soluble material on aerosols collected within volcanic eruption clouds

In February and March of 1978, filter samplers mounted on an aircraft were used to collect the aerosol fraction of the eruption clouds from three active Guatemalan volcanoes (Fuego, Pacaya, and Santiaguito). The samples were collected on Teflon (Fluoropore) filters with a nominal pore diameter of 0.5μm. The mass of air sampled by the filters ranged from 0.15 to 6.6 kg. The particulate material collected consisted of fragments of angular silicate ash and droplets of what is interpreted as dilute H 2 SO 4 and HCl. After collection of the samples, each filter was rinsed with 60 ml of distilled-deionized water. Splits of each extract were centrifuged to remove particles greater than or equal to 0.1 μm in diameter, acidified, and analyzed for B, Ba, Be, Ca, Cd, Co, Cu, Fe, Li, Mg, Mn, Mo, Na, Pb, Si, Sr, V, and Zn by inductively coupled plasma—optical emission spectroscopy. Separate splits were analyzed for F and Cl by specific-ion-electrode methods and for U by a fission track technique. The elements dissolved in the aqueous extracts represent components of water-soluble material either formed directly in the eruption cloud or derived from interaction of ash particles and aerosol components of the plume. Calculations of enrichment factors, based upon concentration ratios, showed the elements most enriched in the extracts relative to bulk ash composition were Cd, Cu, V, F, Cl, Zn, and Pb. These elements represent a subset (with the addition of Cl and F) of elements previously reported enriched in atmospheric aerosols in remote regions as well as in volcanic areas. This suggests that some of the enriched elements were widely dispersed as volatile halides emitted from a volcanic source.

Journal of Geophysical Research - Oceans

Evidence for a subsurface ocean on Europa

Ground-based spectroscopy of Jupiter's moon Europa, combined with gravity data, suggests that the satellite has an icy crust roughly 150 km thick and a rocky interior. In addition, images obtained by the Voyager spacecraft revealed that Europa's surface is crossed by numerous intersecting ridges and dark bands (called lineae) and is sparsely cratered, indicating that the terrain is probably significantly younger than that of Ganymede and Callisto. It has been suggested that Europa's thin outer ice shell might be separated from the moon's silicate interior by a liquid water layer, delayed or prevented from freezing by tidal heating; in this model, the lineae could be explained by repetitive tidal deformation of the outer ice shell. However, observational confirmation of a subsurface ocean was largely frustrated by the low resolution (>2 km per pixel) of the Voyager images. Here we present high-resolution (54 m per pixel) Galileo spacecraft images of Europa, in which we find evidence for mobile 'icebergs'. The detailed morphology of the terrain strongly supports the presence of liquid water at shallow depths below the surface, either today or at some time in the past. Moreover, lower- resolution observations of much larger regions suggest that the phenomena reported here are widespread.

Nature

Microbial formation of labile organic carbon in Antarctic glacial environments

Roughly six petagrams of organic carbon are stored within ice worldwide. This organic carbon is thought to be of old age and highly bioavailable. Along with storage of ancient and new atmospherically deposited organic carbon, microorganisms may contribute substantially to the glacial organic carbon pool. Models of glacial microbial carbon cycling vary from net respiration to net carbon fixation. Supraglacial streams have not been considered in models although they are amongst the largest ecosystems on most glaciers and are inhabited by diverse microbial communities. Here we investigate the biogeochemical sequence of organic carbon production and uptake in an Antarctic supraglacial stream in the McMurdo Dry Valleys using nanometre-scale secondary ion mass spectrometry, fluorescence spectroscopy, stable isotope analysis and incubation experiments. We find that heterotrophic production relies on highly labile organic carbon freshly derived from photosynthetic bacteria rather than legacy organic carbon. Exudates from primary production were utilized by heterotrophs within 24 h, and supported bacterial growth demands. The tight coupling of microbially released organic carbon and rapid uptake by heterotrophs suggests a dynamic local carbon cycle. Moreover, as temperatures increase there is the potential for positive feedback between glacial melt and microbial transformations of organic carbon.

Nature Geoscience

Semantic segmentation of light-toned veins in multimodal ChemCam data

Since the Mars Science Laboratory landed in 2012, the ChemCam instrument aboard the rover has collected in-situ laser-induced breakdown spectroscopy (LIBS) data and context images along more than 35 km of the Gale Crater traverse, providing valuable observations including diagenetic features such as light-toned veins. These veins are of particular scientific interest because they are interpreted as indicators of past fluid circulation on Mars and provide insights into the evolution of habitability on Mars. Their identification, however, currently relies on manual visual inspection of Remote Micro Imager (RMI) images, a process that is time-consuming and sensitive to differences in human interpretation. To address this issue, in this paper we introduce a novel pixel-level labeled, multimodal dataset of ChemCam observations specifically tailored for vein detection, along with customized U-Net models to integrate both textural (RMI) and chemical (LIBS) modalities. To further ensure trustworthy scientific use, we incorporate the Learn-Then-Test (LTT) framework to provide statistical control of the false discovery rate without requiring model retraining. The experimental results demonstrate that the proposed customized U-Net models trained on the developed dataset, combined with risk-controlled prediction, increases the efficiency of pixel-level vein identification through automation and produces statistically reliable predictions for multimodal ChemCam data.

Scientific Reports

Spectrally monitoring the response of the biocrust moss Syntrichia caninervis to altered precipitation regimes

Climate change is expected to impact drylands worldwide by increasing temperatures and changing precipitation patterns. These effects have known feedbacks to the functional roles of dryland biological soil crust communities (biocrusts), which are expected to undergo significant climate-induced changes in community structure and function. Nevertheless, our ability to monitor the status and physiology of biocrusts with remote sensing is limited due to the heterogeneous nature of dryland landscapes and the desiccation tolerance of biocrusts, which leaves them frequently photosynthetically inactive and difficult to assess. To address this critical limitation, we subjected a dominant biocrust species Syntrichia caninervis to climate-induced stress in the form of small, frequent watering events, and spectrally monitored the dry mosses’ progression towards mortality. We found points of spectral sensitivity responding to experimentally-induced stress in desiccated mosses, indicating that spectral imaging is an effective tool to monitor photosynthetically inactive biocrusts. Comparing the Normalized Difference Vegetation Index (NDVI), the Simple Ratio (SR), and the Normalized Pigment Chlorophyll Index (NPCI), we found NDVI minimally effective at capturing stress in precipitation-stressed dry mosses, while the SR and NPCI were highly effective. Our results suggest the strong potential for utilizing spectroscopy and chlorophyll-derived indices to monitor biocrust ecophysiological status, even when biocrusts are dry, with important implications for improving our understanding of dryland functioning.

Scientific Reports

Hydration free energies of cyanide and hydroxide ions from molecular dynamics simulations with accurate force fields

The evaluation of hydration free energies is a sensitive test to assess force fields used in atomistic simulations. We showed recently that the vibrational relaxation times, 1D- and 2D-infrared spectroscopies for CN(-) in water can be quantitatively described from molecular dynamics (MD) simulations with multipolar force fields and slightly enlarged van der Waals radii for the C- and N-atoms. To validate such an approach, the present work investigates the solvation free energy of cyanide in water using MD simulations with accurate multipolar electrostatics. It is found that larger van der Waals radii are indeed necessary to obtain results close to the experimental values when a multipolar force field is used. For CN(-), the van der Waals ranges refined in our previous work yield hydration free energy between -72.0 and -77.2 kcal mol(-1), which is in excellent agreement with the experimental data. In addition to the cyanide ion, we also study the hydroxide ion to show that the method used here is readily applicable to similar systems. Hydration free energies are found to sensitively depend on the intermolecular interactions, while bonded interactions are less important, as expected. We also investigate in the present work the possibility of applying the multipolar force field in scoring trajectories generated using computationally inexpensive methods, which should be useful in broader parametrization studies with reduced computational resources, as scoring is much faster than the generation of the trajectories.

Physical Chemistry Chemical Physics

ChemCam activities and discoveries during the nominal mission of the Mars Science Laboratory in Gale crater, Mars

At Gale crater, Mars, ChemCam acquired its first laser-induced breakdown spectroscopy (LIBS) target on Sol 13 of the landed portion of the mission (a Sol is a Mars day). Up to Sol 800, more than 188 000 LIBS spectra were acquired on more than 5800 points distributed over about 650 individual targets. We present a comprehensive review of ChemCam scientific accomplishments during that period, together with a focus on the lessons learned from the first use of LIBS in space. For data processing, we describe new tools that had to be developed to account for the uniqueness of Mars data. With regard to chemistry, we present a summary of the composition range measured on Mars for major-element oxides (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O) based on various multivariate models, with associated precisions. ChemCam also observed H, and the non-metallic elements C, O, P, and S, which are usually difficult to quantify with LIBS. F and Cl are observed through their molecular lines. We discuss the most relevant LIBS lines for detection of minor and trace elements (Li, Rb, Sr, Ba, Cr, Mn, Ni, and Zn). These results were obtained thanks to comprehensive ground reference datasets, which are set to mimic the expected mineralogy and chemistry on Mars. With regard to the first use of LIBS in space, we analyze and quantify, often for the first time, each of the advantages of using stand-off LIBS in space: no sample preparation, analysis within its petrological context, dust removal, sub-millimeter scale investigation, multi-point analysis, the ability to carry out statistical surveys and whole-rock analyses, and rapid data acquisition. We conclude with a discussion of ChemCam performance to survey the geochemistry of Mars, and its valuable support of decisions about selecting where and whether to make observations with more time and resource-intensive tools in the rover's instrument suite. In the end, we present a bird's-eye view of the many scientific results: discovery of felsic Noachian crust, first observation of hydrated soil, discovery of manganese-rich coatings and fracture fills indicating strong oxidation potential in Mars' early atmosphere, characterization of soils by grain size, and wide scale mapping of sedimentary strata, conglomerates, and diagenetic materials.

Journal of Analytical Atomic Spectrometry

Accuracy of methods for reporting inorganic element concentrations and radioactivity in oil and gas wastewaters from the Appalachian Basin, U.S. based on an inter-laboratory comparison.

Accurate and precise analyses of oil and gas (O&G) wastewaters and solids ( e.g. , sediments and sludge) are important for the regulatory monitoring of O&G development and tracing potential O&G contamination in the environment. In this study, 15 laboratories participated in an inter-laboratory comparison on the chemical characterization of three O&G wastewaters from the Appalachian Basin and four solids impacted by O&G development, with the goal of evaluating the quality of data and the accuracy of measurements for various analytes of concern. Using a variety of different methods, analytes in the wastewaters with high concentrations ( i.e. , >5 mg L −1 ) were easily detectable with relatively high accuracy, often within ±10% of the most probable value (MPV). In contrast, often less than 7 of the 15 labs were able to report detectable trace metal(loid) concentrations ( i.e. , Cr, Ni, Cu, Zn, As, and Pb) with accuracies of approximately ±40%. Despite most labs using inductively coupled plasma mass spectrometry (ICP-MS) with low instrument detection capabilities for trace metal analyses, large dilution factors during sample preparation and low trace metal concentrations in the wastewaters limited the number of quantifiable determinations and likely influenced analytical accuracy. In contrast, all the labs measuring Ra in the wastewaters were able to report detectable concentrations using a variety of methods including gamma spectroscopy and wet chemical approaches following Environmental Protection Agency (EPA) standard methods. However, the reported radium activities were often greater than ±30% different to the MPV possibly due to calibration inconsistencies among labs, radon leakage, or failing to correct for self-attenuation. Reported radium activities in solid materials had less variability (±20% from MPV) but accuracy could likely be improved by using certified radium standards and accounting for self-attenuation that results from matrix interferences or a density difference between the calibration standard and the unknown sample. This inter-laboratory comparison illustrates that numerous methods can be used to measure major cation, minor cation, and anion concentrations in O&G wastewaters with relatively high accuracy while trace metal(loid) and radioactivity analyses in liquids may often be over ±20% different from the MPV.

Appalachian Basin

Discovery and potential ramifications of reduced iron-bearing nanoparticles — Magnetite, wüstite, and zero-valent iron — In wildland–urban interface fire ashes

The increase in fires at the wildland–urban interface has raised concerns about the potential environmental impact of ash remaining after burning. Here, we examined the concentrations and speciation of iron-bearing nanoparticles in wildland–urban interface ash. Total iron concentrations in ash varied between 4 and 66 mg g −1 . Synchrotron X-ray absorption near-edge structure (XANES) spectroscopy of bulk ash samples was used to quantify the relative abundance of major Fe phases, which were corroborated by transmission electron microscopy measurements. Maghemite (γ-(Fe 3+ ) 2 O 3 ) and magnetite (γ-Fe 2+ (Fe 3+ ) 2 O 4 ) were detected in most ashes and accounted for 0–90 and 0–81% of the spectral weight, respectively. Ferrihydrite (amorphous Fe( III )–hydroxide, (Fe 3+ ) 5 HO 8 ·4H 2 O), goethite (α-Fe 3+ OOH), and hematite (α-Fe 3+ 2 O 3 ) were identified less frequently in ashes than maghemite and magnetite and accounted for 0–65, 0–54, and 0–50% of spectral weight, respectively. Other iron phases identified in ashes include wüstite (Fe 2+ O), zerovalent iron, FeS, FeCl 2 , FeCl 3 , FeSO 4 , Fe 2 (SO 4 ) 3 , and Fe(NO 3 ) 3 . Our findings demonstrate the impact of fires at the wildland–urban interface on iron speciation; that is, fires can convert iron oxides ( e.g. , maghemite, hematite, and goethite) to reduced iron phases such as magnetite, wüstite, and zerovalent iron. Magnetite concentrations ( e.g. , up to 25 mg g −1 ) decreased from black to gray to white ashes. Based on transmission electron microscopy (TEM) analyses, most of the magnetite nanoparticles were less than 500 nm in size, although larger particles were identified. Magnetite nanoparticles have been linked to neurodegenerative diseases as well as climate change. This study provides important information for understanding the potential environmental impacts of fires at the wildland–urban interface, which are currently poorly understood.

Environmental Science Nano

Adsorption of goethite onto quartz and kaolinite

The adsorption of colloidal goethite onto quartz and kaolinite substrates has been studied as a function of pH and NaCl concentration. Goethite adsorption was measured quantitatively by Fourier-transform infrared spectroscopy. The results indicate that adsorption onto both substrates is due primarily to coulombic forces; however, the pH dependence of adsorption is very different for the two substrates. This is explained by the fact that the surface charge on quartz is entirely pH-dependent, while kaolinite has surface faces which carry a permanent negative charge. Adsorption of goethite on to kaolinite increases markedly with increasing NaCl concentration, while adsorption onto quartz is relatively independent of NaCl concentration. This can be explained by the influence of NaCl concentration upon the development of surface charge on the substrates. A method is described for separating surface-bound goethite from free goethite.

Journal of the Chemical Society, Faraday Transacti

2D IR spectra of cyanide in water investigated by molecular dynamics simulations

Using classical molecular dynamics simulations, the 2D infrared (IR) spectroscopy of CN − solvated in D 2 O is investigated. Depending on the force field parametrizations, most of which are based on multipolar interactions for the CN − molecule, the frequency-frequency correlation function and observables computed from it differ. Most notably, models based on multipoles for CN − and TIP3P for water yield quantitatively correct results when compared with experiments. Furthermore, the recent finding that T 1 times are sensitive to the van der Waals ranges on the CN − is confirmed in the present study. For the linear IR spectrum, the best model reproduces the full widths at half maximum almost quantitatively (13.0 cm −1 vs. 14.9 cm −1 ) if the rotational contribution to the linewidth is included. Without the rotational contribution, the lines are too narrow by about a factor of two, which agrees with Raman and IR experiments. The computed and experimental tilt angles (or nodal slopes) α as a function of the 2D IR waiting time compare favorably with the measured ones and the frequency fluctuation correlation function is invariably found to contain three time scales: a sub-ps, 1 ps, and one on the 10-ps time scale. These time scales are discussed in terms of the structural dynamics of the surrounding solvent and it is found that the longest time scale (≈10 ps) most likely corresponds to solvent exchange between the first and second solvation shell, in agreement with interpretations from nuclear magnetic resonance measurements.

Journal of Chemical Physics

Mineralogy and arsenic mobility in arsenic-rich Brazilian soils and sediments

Background. Soils and sediments in certain mining regions of Brazil contain an unusually large amount of arsenic (As), which raises concerns that mining could promote increased As mobility, and thereby increase the risks of contaminating water supplies. Objectives. The purpose of t his study was to identify the most important factors governing As mobility in sediments and soils near three gold-mining sites in the State of Minas Gerais, Brazil. Methods. Surface and sub-surface soil samples were collected at those sites and characterized by chemical and mineralogical analyses. Oxalate (Feo) and citrate-bicarbonate-dithionite (Fed) iron contents were determined by atomic absorption spectroscopy (AAS). Arsenic mobilization was measured after incubating the samples in a 2.5 mM CaCl2 solution under anaerobic conditions for 1, 28, 56, 84, or 112 days. The solution concentrations of As, Fe, and Mn were then measured by inductively coupled plasma-mass spectrometry (ICP-MS) and AAS, respectively. Results and Discussion. Results indicated that As mobilization is largely independent of both the total As and the Feo/Fed ratio of the solid phase. Soluble As is roughly controlled by the Fe (hydr)oxide content of the soil, but a closer examination of the data revealed the importance of other highly weathered clay minerals and organic matter. Large amounts of organic matter and a low iron oxide content should favor As leaching from soils and sediments. Under reducing conditions, As is mobilized by the reductive dissolution of Fe and/or Mn oxides. However, released As may be readsorbed depending on the sorptive properties of the soil. Gibbsite is particularly effective in adsorbing or readsorbing As, as is the remaining unreduced fraction of the iron (hydr)oxides. Conclusion and Outlook. In general, low soluble As is rel ated to the presence of gibbsite, a large amount of iron oxides, and a lack of organic matter in the solid phase. This has environmental significance because gibbsite is thermodynamically more stable than Fe oxides under anaerobic conditions, such as those found in waterlogged soils and lake sediments. ?? 2006 ecomed publishers (Verlagsgruppe Hu??thig Jehle Rehm GmbH), D-86899 Landsberg and Tokyo.

Journal of Soils and Sediments

Surficial geochemistry and bioaccessibility of tellurium in semi-arid mine tailings

Tellurium (Te) is a critical element due to its use in solar technology. However, some forms are highly toxic. Few studies have examined Te behavior in the surficial environment, thus little is known about its potential human and environmental health impacts. This study characterizes two physicochemically distinct Te-enriched mine tailings piles (big and flat tailings) deposited by historic gold (Au) mining in the semi-arid Delamar mining district, Nevada. The big tailings are characterized by smaller particle size and higher concentrations of potentially toxic elements (up to 290 mg Te kg-1), which are enriched at the tailings surface. In contrast, the flat tailings have larger particle size and properties that are relatively invariant with depth. Based on the sulfate to sulfide ratio, the tailings were determined to be sulfate dominated suggesting a high degree of weathering, although the flat tailings did contain significant amounts of sulfides (~40%). Tellurium x-ray absorption spectroscopy of the big tailings indicates that tellurate, the less toxic Te species, is the principal form of Te. Electron microscopy indicates that most of the Te present at the site is associated with iron (oxy)hydroxides, sometimes with other potentially toxic elements, especially lead and antimony. Physiologically-based extraction tests indicate that substantially more Te is solubilized in synthetic stomach fluids than in lung fluids, with gastric bioaccessibility ranging from 13-31% of total Te. This points to low to medium bioaccessibility, which is common for iron (oxy)hydroxide associated elements. Together, these results represent a preliminary assessment of Te surficial behavior in a semi-arid environment and indicate that Te in these tailings represent a moderate health concern.

Environmental Chemistry