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USGS2001

A procedural manual for measurement of uranium and thorium isotopes utilizing the USGS-Stanford Finnegan Mat 262

Over the past several decades investigators have extensively examined the 238U-234U- 230Th systematics of a variety of geologic materials using alpha spectroscopy. Analytical uncertainty for 230Th by alpha spectroscopy has been limited to about 2% (2σ). The advantage of thermal ionization mass spectroscopy (TIMS), introduced by Edwards and co-workers in the late 1980’s is the increased detectability of these isotopes by a factor of ~200, and decreases in the uncertainty for 230Th to about 5‰ (2σ) error. This report is a procedural manual for using the USGS-Stanford Finnegan-Mat 262 TIMS to collect and isolate Uranium and Thorium isotopic ratio data. Chemical separation of Uranium and Thorium from the sample media is accomplished using acid dissolution and then processed using anion exchange resins. The Finnegan-Mat262 Thermal Ionization Mass Spectrometer (TIMS) utilizes a surface ionization technique in which nitrates of Uranium and Thorium are placed on a source filament. Upon heating, positive ion emission occurs. The ions are then accelerated and focused into a beam which passes through a curved magnetic field dispersing the ions by mass. Faraday cups and/or an ion counter capture the ions and allow for quantitative analysis of the various isotopes.

Open-File Report↗

USGS2001

Environmental studies of the World Trade Center area after the September 11, 2001 attack

This web site describes the results of an interdisciplinary environmental characterization of the World Trade Center (WTC) area after September 11, 2001. Information presented in this site was first made available to the World Trade Center emergency response teams on September 18, 2001 (Thermal hot spot information), and September 27, 2001 (maps and compositional results). The Airborne Visible / Infrared Imaging Spectrometer (AVIRIS), a hyperspectral remote sensing instrument, was flown by JPL/NASA over the World Trade Center (WTC) area on September 16, 18, 22, and 23, 2001 ( Link to the AVIRIS JPL data facility) . A 2-person USGS crew collected samples of dusts and airfall debris from more than 35 localities within a 1-km radius of the World trade Center site on the evenings of September 17 and 18, 2001. Two samples were collected of indoor locations that were presumably not affected by rainfall (there was a rainstorm on September 14). Two samples of material coating a steel beam in the WTC debris were also collected. The USGS ground crew also carried out on-the-ground reflectance spectroscopy measurements during daylight hours to field calibrate AVIRIS remote sensing data. Radiance calibration and rectification of the AVIRIS data were done at JPL/NASA. Surface reflectance calibration, spectral mapping, and interpretation were done at the USGS Imaging Spectroscopy Lab in Denver. The dust/debris and beam-insulation samples were analyzed for a variety of mineralogical and chemical parameters using Reflectance Spectroscopy (RS), Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), chemical analysis, and chemical leach test techniques in U.S. Geological Survey laboratories in Denver, Colorado.

New York↗

USGS2012

Concentrations of mercury and other metals in black bass (Micropterus spp.) from Whiskeytown Lake, Shasta County, California, 2005

This report presents the results of a reconnaissance study conducted by the U.S. Geological Survey (USGS) to determine mercury (Hg) and other selected metal concentrations in Black bass ( Micropterus spp. ) from Whiskeytown Lake, Shasta County, California. Total mercury concentrations were determined by cold-vapor atomic absorption spectroscopy (CVAAS) in fillets and whole bodies of each sampled fish. Selected metals scans were performed on whole bodies (less the fillets) by inductively coupled plasma–mass spectroscopy (ICP-MS) and inductively coupled plasma–optical emission spectroscopy (ICP-OES). Mercury concentrations in fillet samples ranged from 0.06 to 0.52 micrograms per gram (μg/g) wet weight (ww). Total mercury (HgT) in the same fish whole-body samples ranged from 0.04 to 0.37 (μg/g, ww). Mercury concentrations in 17 percent of "legal catch size" (≥305 millimeters in length) were above the U.S. Environmental Protection Agency water-quality criterion for the protection of human health of 0.30 μg/g (ww). These data will serve as a baseline for future monitoring efforts within Whiskeytown Lake.

California↗

USGS2014

The Tetracorder user guide: version 4.4

Imaging spectroscopy mapping software assists in the identification and mapping of materials based on their chemical properties as expressed in spectral measurements of a planet including the solid or liquid surface or atmosphere. Such software can be used to analyze field, aircraft, or spacecraft data; remote sensing datasets; or laboratory spectra. Tetracorder is a set of software algorithms commanded through an expert system to identify materials based on their spectra (Clark and others, 2003). Tetracorder also can be used in traditional remote sensing analyses, because some of the algorithms are a version of a matched filter. Thus, depending on the instructions fed to the Tetracorder system, results can range from simple matched filter output, to spectral feature fitting, to full identification of surface materials (within the limits of the spectral signatures of materials over the spectral range and resolution of the imaging spectroscopy data). A basic understanding of spectroscopy by the user is required for developing an optimum mapping strategy and assessing the results.

Open-File Report↗

USGS2024

Enhanced petrogenic organic carbon oxidation during the Paleocene-Eocene thermal maximum

The Paleocene-Eocene thermal maximum (PETM; ∼56 Ma) is a hyperthermal event associated with the rapid input of carbon into the ocean-atmosphere system. The oxidation of petrogenic organic carbon (OC petro ) may have released additional carbon dioxide (CO 2 ), thereby prolonging the PETM. However, proxy-based estimates of OC petro oxidation are unavailable due to the lack of suitable techniques. Raman spectroscopy is used to evaluate OC petro oxidation in modern settings. For the first time, we explore whether Raman spectroscopy can evaluate OC petro oxidation during the PETM. In the mid-Atlantic Coastal Plain, there is a shift from disordered to graphitised carbon. This is consistent with enhanced oxidation of disordered OC petro and intensified physical erosion. In the Arctic Ocean, the distribution of graphitised carbon vs . disordered carbon does not change, suggesting limited variability in weathering intensity. Overall, this study provides the first evidence of increased OC petro oxidation during the PETM, although it was likely not globally uniform. Our work also highlights the utility of Raman spectroscopy as a novel tool to reconstruct OC petro oxidation in the past.

Geochemical Perspectives Letters↗

USGS1990

Multielement extraction system for determining 19 trace elements in gold exploration samples

A multielement extraction system is being used successfully to provide essentially interference-free geochemical analyses to aid in gold exploration. The Methyl isobutyl ketone-Amine synerGistic Iodide Complex (MAGIC) extraction system separates Ag, As, Au, Bi, Cd, Cu, Ga, Hg, In, Mo, Pb, Pd, Pt, Sb, Se, Sn, Te, Tl, and Zn from interfering geological matrices. Quantitative extraction of these elements is accomplished over a broad range of acid normality making it possible to economically determine all 19 elements from a single digestion or leach solution. The resulting organic extracts are amenable to analysis by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and flame atomic absorption spectroscopy (FAAS). For many years the principal shortcoming of ICP-AES was the complex spectral and stray-light interferences that were caused by the extreme variability of components such as Fe, Na, and Ca in common geological matrices. The MAGIC extraction allows determination of the extracted elements with enhanced sensitivity, from a virtually uniform matrix, by ICP-AES and FAAS. Because of its simultaneous multichannel capabilities, ICP-AES is the ideal instrumental technique for determining these 19 extracted elements. Ultratrace (sub-part-per-billion) determinations of Au and many of the other extracted elements can be made by graphite furnace atomic absorption spectroscopy (GFAAS), following back stripping of the extracts. The combination of the extraction followed by stripping of the organic phase eliminates 99.999% of potential interferences for Au. Gold determination by GFAAS from these extracts under the specified conditions yields a fourfold improvement in sensitivity over conventional GFAAS methods. This sensitivity enhancement and the interference-free matrix allow highly reliable determinations well into the parts-per-trillion range.

Conference Paper↗

USGS2006

Coupling chemical weathering with soil production across soil-mantled landscapes

Soil-covered upland landscapes constitute a critical part of the habitable world. Our understanding of how they evolve as a function of different climatic, tectonic and geological regimes is important across a wide range of disciplines and depends, in part, on understanding the links between chemical and physical weathering processes. Extensive previous work has shown that soil production rates decrease with increasing soil column thickness, but chemical weathering rates were not measured. Here we examine a granitic, soil-mantled hillslope at Point Reyes, California, where soil production rates were determined using in situ produced cosmogenic nuclides ( 10 Be and 26 Al), and we quantify the extent as well as the rates of chemical weathering of the saprolite from beneath soil from across the landscape. We collected saprolite samples from the base of soil pits and analysed them for abrasion pH as well as for major and trace elements by X-ray fluorescence spectroscopy, and for clay mineralogy by X-ray diffraction spectroscopy. Our results show for the first time that chemical weathering rates decrease with increasing soil thickness and account for 13 to 51 per cent of total denudation. We also show that spatial variation in chemical weathering appears to be topographically controlled: weathering rate decreases with slope across the divergent ridge and increases with upslope contributing area in the convergent swale. Furthermore, to determine the best measure for the extent of saprolite weathering, we compared four different chemical weathering indices – the Vogt ratio, the chemical index of alteration (CIA), Parker's index, and the silicon–aluminium ratio – with saprolite pH. Measurements of the CIA were the most closely correlated with saprolite pH, showing that weathering intensity decreases linearly with an increase in saprolite pH from 4·7 to almost 7. Data presented here are among the first to couple directly rates of soil production and chemical weathering with how topography is likely to control weathering at a hillslope scale.

Earth Surface Processes and Landforms↗

USGS2000

Europa's Crust and Ocean: Origin, Composition, and the Prospects for Life

We have considered a wide array of scenarios for Europa's chemical evolution in an attempt to explain the presence of ice and hydrated materials on its surface and to understand the physical and chemical nature of any ocean that may lie below. We postulate that, following formation of the jovian system, the europan evolutionary sequence has as its major links: (a) initial carbonaceous chondrite rock, (b) global primordial aqueous differentiation and formation of an impure primordial hydrous crust, (c) brine evolution and intracrustal differentiation, (d) degassing of Europa's mantle and gas venting, (e) hydrothermal processes, and (f) chemical surface alteration. Our models were developed in the context of constraints provided by Galileo imaging, near infrared reflectance spectroscopy, and gravity and magnetometer data. Low-temperature aqueous differentiation from a carbonaceous CI or CM chondrite precursor, without further chemical processing, would result in a crust/ocean enriched in magnesium sulfate and sodium sulfate, consistent with Galileo spectroscopy. Within the bounds of this simple model, a wide range of possible layered structures may result; the final state depends on the details of intracrustal differentiation. Devolatilization of the rocky mantle and hydrothermal brine reactions could have produced very different ocean/crust compositions, e.g., an ocean/crust of sodium carbonate or sulfuric acid, or a crust containing abundant clathrate hydrates. Realistic chemical-physical evolution scenarios differ greatly in detailed predictions, but they generally call for a highly impure and chemically layered crust. Some of these models could lead also to lateral chemical heterogeneities by diapiric upwellings and/or cryovolcanism. We describe some plausible geological consequences of the physical-chemical structures predicted from these scenarios. These predicted consequences and observed aspects of Europa's geology may serve as a basis for further analys is and discrimination among several alternative scenarios. Most chemical pathways could support viable ecosystems based on analogy with the metabolic and physiological versatility of terrestrial microorganisms. ?? 2000 Academic Press.

Icarus↗

USGS2023

Insights into the metamorphic history and origin of flake graphite mineralization at the Graphite Creek graphite deposit, Seward Peninsula, Alaska, USA

Graphite Creek is an unusual flake graphite deposit located on the Seward Peninsula, Alaska, USA. We present field observations, uranium-lead (U–Pb) monazite and titanite geochronology, carbon (C) and sulfur (S) stable isotope geochemistry, and graphite Raman spectroscopy data from this deposit that support a new model of flake graphite ore genesis in high-grade metamorphic environments. The Graphite Creek deposit is within the second sillimanite metamorphic zone of the Kigluaik Mountains gneiss dome. Flake graphite, hosted in sillimanite-gneiss and quartz-biotite paragneiss, occurs as disseminations and in sets of very high grade (up to 50 wt.% graphite), semi-massive to massive graphite lenses 0.2 to 1 m wide containing quartz, sillimanite, inclusions of garnet porphyroblasts, K-feldspar, and tourmaline. Restitic garnet, sillimanite, graphite, and biotite accumulations indicate a high degree of anatexis and melt loss. Strong yttrium depletion in monazite, high europium ratios (Eu/Eu*), and excursions of high strontium and thorium concentrations are consistent with biotite dehydration melting. Monazite and titanite U–Pb ages record peak metamorphism from ~ 97 to 92 million years ago (Ma) and a retrograde event at ~ 85 Ma. Raman spectroscopy confirms the presence of carbonaceous material and highly ordered, crystalline graphite. Graphite δ 13 C VPDB values of − 30 to − 12‰ and pyrrhotite δ 34 S VCDT values of − 14 to 10‰ are consistent with derivation from organic carbon and sulfur in sedimentary rocks, respectively. These data collectively suggest that formation of massive graphite lenses occurred approximately synchronously with high-temperature metamorphism and anatexis of a highly carbonaceous pelitic protolith. Melt extraction and fluid release associated with anatexis were likely crucial for concentrating graphite. High-temperature, graphitic migmatite sequences within high-strain shear zones may be favorable for the occurrence of high-grade flake graphite deposits.

Alaska↗

USGS2007

Concentrations of metals in blood and feathers of nestling ospreys (Pandion haliaetus) in Chesapeake and Delaware Bays

In 2000, 2001, and 2002, blood and feather samples were collected from 40–45-day-old nestling ospreys ( Pandion haliaetus ) from Chesapeake Bay and Delaware Bay and River. Concentrations of 18 metals, metalloids, and other elements were determined in these samples by inductively coupled plasma-mass spectroscopy, and Hg concentrations were measured by cold vapor atomic absorption spectroscopy. When compared to concurrent reference areas (South, West, and Rhode Rivers), mean As and Hg concentrations in blood were greater ( p < 0.05) in two of three Chesapeake Bay regions of concern (Baltimore Harbor [As: 1.18 vs. 0.548 μg/g dw], Anacostia River [Hg: 0.305 vs. 0.178 μg/g dw], and Elizabeth River [As: 0.876 vs. 0.663 μg/g dw; Hg: 0.260 vs. 0.180 μg/g dw]). Lead was detected more frequently in blood of nestlings from the highly industrialized Elizabeth River compared to the rural reference area. When compared to the concurrent reference area, mean Al, Ba, Hg, Mn, and Pb concentrations in feathers were substantially greater ( p < 0.05) in one or more Chesapeake regions of concern (Anacostia River [Al: 206 vs. 62.1 μg/g dw; Ba: 3.31 vs. 0.823 μg/g dw; Mn: 65.4 vs. 22.9 μg/g dw] and Elizabeth River [Al: 165 vs. 63.5 μg/g dw; Hg: 1.24 vs. 0.599 μg/g dw; Pb 1.47 vs. 0.543 μg/g dw]). When compared to the coastal Inland Bays reference area, feathers of nestlings from northern Delaware Bay and River had greater concentrations ( p < 0.05) of Ba (1.90 vs. 0.660 μg/g dw), Fe (258 vs. 109 μg/g dw), Mn (18.5 vs. 4.66 μg/g dw), Mo (0.130 vs. 0.040 μg/g dw), Pb (1.96 vs. 0.624 μg/g dw), and V (0.671 vs. 0.325 μg/g dw), presumably due to extensive metal-working and petroleum refinery activities. Concentrations of Hg in nestling feathers from Delaware were frequently greater than in the Chesapeake. The present findings and those of related reproductive studies suggest that concentrations of several heavy metals (e.g., Cd, Hg, Pb) in nestling blood and feathers from Chesapeake and Delaware Bays were below toxicity thresholds and do not seem to be affecting chick survival during the nestling period.

Delaware, Maryland, New Jersey, Virginia↗

USGS2012

The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Science objectives and mast unit description

ChemCam is a remote sensing instrument suite on board the "Curiosity" rover (NASA) that uses Laser-Induced Breakdown Spectroscopy (LIBS) to provide the elemental composition of soils and rocks at the surface of Mars from a distance of 1.3 to 7 m, and a telescopic imager to return high resolution context and micro-images at distances greater than 1.16 m. We describe five analytical capabilities: rock classification, quantitative composition, depth profiling, context imaging, and passive spectroscopy. They serve as a toolbox to address most of the science questions at Gale crater. ChemCam consists of a Mast-Unit (laser, telescope, camera, and electronics) and a Body-Unit (spectrometers, digital processing unit, and optical demultiplexer), which are connected by an optical fiber and an electrical interface. We then report on the development, integration, and testing of the Mast-Unit, and summarize some key characteristics of ChemCam. This confirmed that nominal or better than nominal performances were achieved for critical parameters, in particular power density (>1 GW/cm 2 ). The analysis spot diameter varies from 350 μm at 2 m to 550 μm at 7 m distance. For remote imaging, the camera field of view is 20 mrad for 1024×1024 pixels. Field tests demonstrated that the resolution (˜90 μrad) made it possible to identify laser shots on a wide variety of images. This is sufficient for visualizing laser shot pits and textures of rocks and soils. An auto-exposure capability optimizes the dynamical range of the images. Dedicated hardware and software focus the telescope, with precision that is appropriate for the LIBS and imaging depths-of-field. The light emitted by the plasma is collected and sent to the Body-Unit via a 6 m optical fiber. The companion to this paper (Wiens et al. this issue) reports on the development of the Body-Unit, on the analysis of the emitted light, and on the good match between instrument performance and science specifications.

Space Science Reviews↗

USGS1978

Mössbauer spectroscopic investigation of iron species in coal

A series of Herrin No. 6 coal and three coal-derived samples have been examined by Mo??ssbauer spectroscopy. It is established that Mo??ssbauer spectroscopy can be used to identify multiple iron species in a whole coal or an autoclaved char sample without the need to concentrate the minerals to enhance resolution. Our results indicate that there may be an association between the pyrite in raw coal and the coal matrix. This association appears to be broken down when the coal is heated to temperatures as low as 175 ??C. It is also apparent that the iron sulphide present in the whole coal is converted to pyrite at these low temperatures. For our samples, the total quantity of iron species in different coal lithotypes is about the same, but they differ in their distributions. The fusain has the least amount of Fe2+ species when compared to the vitrain or whole-coal sample used. At least two types of nonstoichiometric pyrrhotite are produced in the heat-treated samples. One of these pyrrhotites is unstable and contains dissolved sulphur which is apparently liberated as the temperature is increased. ?? 1978.

Fuel↗

USGS1979

Application of a new Raman microprobe spectrometer to nondestructive analysis of sulfate and other ions in individual phases in fluid inclusions in minerals

Rosasco et al . (1975), reported the first successful application of laser-excited Raman spectroscopy for the identification and nondestructive partial analysis of individual solid, liquid, and gaseous phases in selected fluid inclusions. We report here the results of the application of a new instrument, based on back-scattering, that eliminates many of the previous stringent sample limitations and hence greatly expands the range of applicability of Raman spectroscopy to fluid inclusions. Fluid inclusions in many porphyry copper deposits contain 5–10 μm ‘daughter’ crystals thought to be anhydrite but too small for identification by the previous Raman technique. Using the new instrument, we have verified that such daughter crystals in quartz from Bingham, Utah, are anhydrite. They may form by leakage of hydrogen causing internal autooxidation of sulfide ion. Daughter crystals were also examined in apatite (Durango, Mexico) and emerald (Muzo, Colombia). Valid analyses of sulfur species in solution in small fluid inclusions from ore deposits would be valuable, but are generally impossible by conventional methods. We present a calibration procedure for analyses for SO 4 2− in such inclusions from Bingham, Utah (12,000 ± 4000 ppm ) and Creede, Colo. (probably < 500 ppm). A fetid Brazilian quartz, originally thought to contain liquid H 2 S, is shown to contain only HS − in major amounts.

Geochimica et Cosmochimica Acta↗

USGS1985

A method for the determination of vanadium and iron oxidation states in naturally occurring oxides and silicates

A valence-specific analytical method for determining V 3+ in ore minerals has been developed that involves two steps: dissolution of a mineral sample without disturbing the V 3+ /V tot ratio, followed by determination of V 3+ in the presence of V 4+ . The samples are dissolved in a mixture of hydrofluoric and sulphuric acids at 100° in Teflon-lined reaction vessels. Tervalent vanadium is then determined colorimetrically by formation of a V 3+ -thiocyanate complex in aqueous-acetone medium. Fe 3+ is measured semi-quantitatively in the same solution. The method has been tested with two naturally occurring samples containing vanadium and iron. The results obtained were supported by those obtained by other methods, including electron spin resonance spectroscopy, thermogravimetric analysis, and Mössbauer spectroscopy.

Talanta↗

USGS1986

An analytical scheme for determining forms of sulphur in oil shales and associated rocks

An analytical scheme for determining various forms of sulphur in oil shales and associated rocks is presented. Acid-soluble sulphate, sulphur contained in monosulphide and in disulphide minerals, and organically-bound sulphur are all quantitatively recovered as separate fractions. Finely-ground oil-shale samples are treated in an inert atmosphere with 6 M hydrochloric acid to dissolve the acid-soluble sulphate minerals and form H 2 S from the decomposition of monosulphide minerals. The acid-soluble sulphate is precipitated as barium sulphate and the H 2 S is collected and weighed as silver sulphide. Disulphide minerals in the solid residue from the acid treatment are reduced by an acidified Cr(II) solution in an inert atmosphere, releasing the sulphide as H 2 S. The H 2 S is collected as silver sulphide. An Eschka fusion oxidizes and solubilizes all sulphur remaining within the Cr(II)-treated residue. This sulphate represents organically-bound sulphur and is collected as barium sulphate. The analytical procedures have been verified by using 57 Fe Mössbauer spectroscopy. Good agreement between the chemical and Mössbauer data substantiated the sequential removal of the forms of sulphur and also demonstrated the ability of Mössbauer spectroscopy to determine the absolute quantities of iron present in specific minerals.

Talanta↗

USGS1994

Comparison of humic substances isolated from peatbog water by sorption on DEAE-cellulose and amberlite XAD-2

Aquatic humic substances (AHS) were isolated from peatbog water by adsorption (1) on diethylaminoethyl cellulose (DEAE-C) and (2) on Amberlite XAD-2 (XAD) to compare yields of the methods and the composition of the isolated AHS. To provide a detailed comparison, the isolates were fractionated using size-exclusion and hydrophobic-interaction chromatography on Sephadex G-50. The fractions were characterized by ultraviolet-visible, infrared and 13C-nuclear magnetic spectroscopies and analyzed for elemental, functional-group, carbohydrate and amino acid compositions. More AHS adsorbed onto DEAE-C than onto XAD-2 (94 and 74%, respectively). However, only 76% of the AHS adsorbed onto DEAE-C was recovered using 0.1 M NaOH, whereas 98% of the AHS adsorbed onto XAD was released by consecutive elution with 1 M NH4OH (91%) and methanol (7%). Four main fractions of different composition were obtained from each of the alkali-desorbed AHS samples by Sephadex-gel chromatography. General agreement was found in relative amounts, spectroscopic characteristics and composition of corresponding fractions of both isolates except nitrogen content, which was significantly higher in AHS isolated with XAD, apparently due to the reaction of AHS with NH4OH used for the desorption from the resin.Aquatic humic substances (AHS) were isolated from peatbog water by adsorption (1) on diethylaminoethyl cellulose (DEAE-C) and (2) on Amberlite XAD-2 (XAD) to compare yields of the methods and the composition of the isolated AHS. To provide a detailed comparison, the isolates were fractionated using size-exclusion and hydrophobic-interaction chromatography on Sephadex G-50. The fractions were characterized by ultraviolet-visible, infrared and 13C-nuclear magnetic spectroscopies and analyzed for elemental, functional-group, carbohydrate and amino acid compositions. More AHS adsorbed onto DEAE-C than onto XAD-2 (94 and 74%, respectively). However, only 76% of the AHS adsorbed onto DEAE-C was recovered using 0.1 M NaOH, whereas 98% of the AHS adsorbed onto XAD was released by consecutive elution with 1 M NH4OH (91%) and methanol (7%). Four main fractions of different composition were obtained from each of the alkali-desorbed AHS samples by Sephadex-gel chromatography. General agreement was found in relative amounts, spectroscopic characteristics and composition of corresponding fractions of both isolates except nitrogen content, which was significantly higher in AHS isolated with XAD, apparently due to the reaction of AHS with NH4OH used for the desorption from the resin.

Water Research↗

USGS2016

Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara

Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth’s most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002–0.57 wt%) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM < 0.1 μm. For all examined samples, the average iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4% in magnetite, and 65% in ferric silicates. Structural iron in clay minerals may account for much of the iron in the ferric silicates. We estimate that the mean ferric oxides flux exported from the Bodélé Depression is 0.9 Tg/yr with greater than 50% exported as ferric oxide nanoparticles (<0.1 μm). The high surface-to-volume ratios of ferric oxide nanoparticles once entrained into dust plumes may facilitate increased atmospheric chemical and physical processing and affect iron solubility and bioavailability to marine and terrestrial ecosystems.

Aeolian Research↗

USGS2014

Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe 2 O 3 /FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe 2 (SO 4 ) 3 , Fe 2 (SO 4 ) 3 ·5H 2 O, kornelite, coquimbite, Fe(SO 4 )(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm −1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe 3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe 2+ /[Fe 2+ + Fe 3+ ] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

California↗