Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and Fe Mössbauer spectroscopic study     

Allan Kolker  Frank E. Huggins 《Applied Geochemistry》2007

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O₂ atmosphere; (3) room atmosphere (relative humidity ∼20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and ⁵⁷Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. ⁵⁷Fe Mössbauer spectroscopy also shows a much greater proportion of Fe³⁺ forms (jarosite, Fe³⁺ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.  相似文献   

Optically stimulated luminescence dating of sublittoral and intertidal sediments from Dubai, UAE: Radioactive disequilibria in the uranium decay series   总被引：1，自引：0，他引：1  

Anja Zander  Detlev Degering  Frank Preusser  Haino Uwe Kasper  Helmut Brückner 《Quaternary Geochronology》2007,2(1-4):123-128

Shallow marine and intertidal shell rich sediments from the low coastal plain of Dubai were dated by optically stimulated luminescence. Combined high-resolution gamma spectrometry and ICP–MS analyses revealed significant disequilibria in the ²³⁸U decay series. Time dependent dose rates were modelled for two scenarios including a closed system and an open system with linear U and Ra uptake. OSL ages that were calculated using the linear uptake model are in good agreement with archaeological evidence and radiocarbon datings on shells and wood. The presented results illustrate that luminescence-dating techniques are suitable to set up a chronostratigraphic frame for calcareous coastal environments if an appropriate model is applied to consider the influence of radioactive disequilibria and time dependent dose rates. A comprehensive radionuclide analysis of the sediments is thought necessary to perform geochemically supported dose rate simulations.  相似文献   

Selection and ranking of ground motion models for seismic hazard analysis in the Pyrenees   总被引：1，自引：0，他引：1  

Stéphane Drouet  Frank Scherbaum  Fabrice Cotton  Annie Souriau 《Journal of Seismology》2007,11(1):87-100

The issue addressed in this paper is the objective selection of appropriate ground motion models for seismic hazard assessment in the Pyrenees. The method of Scherbaum et al. (2004a) is applied in order to rank eight published ground motion models relevant to intraplate or to low deformation rate contexts. This method is based on a transparent and data-driven process which quantifies the model fit and also measures how well the underlying model assumptions are met. The method is applied to 15 accelerometric records obtained in the Pyrenees for events of local magnitude between 4.8 and 5.1, corresponding to moment magnitudes ranging from 3.7 to 3.9. Only stations at rock sites are considered. A total of 720 spectral amplitudes are used to rank the selected ground motion models. Some control parameters of these models, such as magnitude and distance definitions, may vary from one model to the other. It is thus important to correct the selected models for their difference with respect to the magnitude and distance definitions used for the Pyrenean data. Our analysis shows that, with these corrections, some of the ground motion models successfully fit the data. These are the Lussou et al. (2001) and the Berge-Thierry et al. (2003) models. According to the selected ground motion models, a possible scenario of a magnitude 6 event is proposed; it predicts response spectra accelerations of 0.08–0.1 g at 1 Hz at a hypocentral distance of 10 km.  相似文献   

DIFFERENTIATING SEMIARID ENVIRONMENTS USING LANDSAT REFLECTANCE INDEXES     

Thomas D. Frank 《The Professional geographer》1985,37(1):36-46

Relationships between Landsat reflectance indexes that extract the individual component contributions of vegetation and the soil background and the composition of a semiarid grassland-shrub environment are examined. The results indicate that two reflectance indexes, the Transformed Vegetation Index (TVI) and the ratio of Landsat MSS6/MSS5, exhibit the highest correlation with vegetation density. The ratio of MSS6/MSS4, the ratio of MSS5/MSS4, and the MSS6 soil background reflectance component (Rgg6) emerge as the best indexes to discriminate between semiarid landscape units. The relationships between reflectance and land cover composition suggest that Landsat reflectance may be useful to monitor temporal and spatial changes in the condition of semiarid vegetation.  相似文献   

Temperature variation of the plasma sheet during substorms     

A.T.Y. Lui  C.-I. Meng  L.A. Frank  K.L. Ackerson  S.-I. Akasofu 《Planetary and Space Science》1981,29(8):837-842

The temperature and density of the plasma in the Earth's distant plasma sheet at the downstream distances of about 20–25 R_e are examined during a high geomagnetic disturbance period. It is shown that the plasma sheet cools when magnetospheric substorm expansion is indicated by the AE index. During cooling, the plasma sheet temperature, T, and the number density, N, are related by $\text{T ∝ N}{}^{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}$ (adiabatic process) in some instances, while by T ∝ N^?1 (isobaric process) in other cases. The total plasma and magnetic pressure decreases when $\text{T ∝ N}{}^{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}$ and increases when T ∝ N^?1. Observation also indicates that the dawn-dusk component of plasma flow is frequently large and comparable to the sunward-tailward flow component near the central plasma sheet during substorms.  相似文献   

Direct observations of low-energy solar electrons associated with a type III solar radio burst     

L. A. Frank  D. A. Gurnett 《Solar physics》1972,27(2):446-465

A highly anisotropic packet of solar electron intensities was observed on 6 April 1971 with a sensitive electrostatic analyzer array on the Earth-orbiting satellite IMP-6. The anisotropies of intensities at electron energies of several keV were factors 10 favoring the expected direction of the interplanetary magnetic lines of force from the Sun. The directional, differential intensities of solar electrons were determined over the energy range 1–40 keV and peak intensities were 10² cm^–2 s^–1 sr^–1 eV^–1 at 2–6 keV. This anisotropic packet of solar electrons was detected at the sattelite for a period of 4200 s and was soon followed by isotropic intensities for a relatively prolonged period. This impulsive emission was associated with the onsets of an optical flare, soft X-ray emission and a radio noise storm at centimeter wavelengths on the western limb of the Sun. Simultaneous measurements of a type III radio noise burst at kilometric wavelengths with a plasma wave instrument on the same satellite showed that the onsets for detectable noise levels ranged from 500 s at 178 kHz to 2700 s at 31.1 kHz. The corresponding drift rate requires a speed of 0.15c for the exciting particles if the emission is at the electron plasma frequency. The corresponding electron energy of 6 keV is in excellent agreement with the above direct observations of the anisotropic electron packet. Further supporting evidence that several-keV solar electrons in the anisotropic packet are associated with the emission of type III radio noise beyond 50R is provided by their time-of-arrival at Earth and the relative durations of the radio noise and the solar electron packet. Electron intensities at E 45 keV and the isotropic intensities of lower-energy solar electrons are relatively uncorrelated with the measurements of type III radio noise at these low frequencies. The implications of these observations relative to those at higher frequencies, and heliocentric radial distances 50R , include apparent deceleration of the exciting electron beam with increasing heliocentric radial distance.Research supported in part by the National Aeronautics and Space Administration under contracts NAS5-11039 and NAS5-11074 and grant NGL16-001-002 and by the Office of Naval Research under contract N000-14-68-A-0196-0003.  相似文献   

Spectral analyses of solar photospheric fluctuations     

Frank N. Edmonds Jr.  Carol J. Webb 《Solar physics》1972,23(1):47-57

Residual intensity fluctuation measurements within the wings of the 5183.6 Mgi b₁ line, obtained from two, high-resolution, high-dispersion, Sacramento Peak Observatory spectrograms, have been subtracted from intensity fluctuations in the adjacent continuum in order to isolate fluctuations associated exclusively with line formation. The useable spectral range for studying these lineformation fluctuations is restricted to wavelengths between 1040 and 7170 km because the subtraction increases the relative importance of noise and large-scale photographic variations across the spectrograms could not be completely removed. Power and cross-power (coherence and phase) spectra proved to be valuable diagnostic tools in isolating line-formation fluctuations.Over this spectral range, the line-formation fluctuations are characterized by flat power spectra as compared to those for continuum fluctuations, appreciable fluctuation rms relative to that for continuum fluctuations, and the necessity to multiply the wing fluctuations by a factor 0.95 _min 1.00 to most effectively isolate these fluctuations (Figures 3 and 4). That continuum fluctuations are modified in shape but otherwise not drastically changed in the line wings explains the flat spectrum. The relative rms's vary from 0.34 in the inner wing to 0.22 in the outer. The range of possible values for _min results from uncertainties in the photographic density-residual intensity calibration.  相似文献   

Transient simulations,empirical reconstructions and forcing mechanisms for the Mid-holocene hydrological climate in southern Patagonia     

Sebastian Wagner  Martin Widmann  Julie Jones  Torsten Haberzettl  Andreas Lücke  Christoph Mayr  Christian Ohlendorf  Frank Schäbitz  Bernd Zolitschka 《Climate Dynamics》2007,29(4):333-355

This study investigates the atmospheric circulation in transient climate simulations with a coupled atmosphere–ocean general circulation model (GCM) for the mid-Holocene (MH) period 7–4.5 ka BP driven with combinations of orbital, solar and greenhouse gas forcings. The focus is on southern South America. Statistical downscaling models are derived from observational data and applied to the simulations to estimate precipitation in south-eastern Patagonia during the MH. These estimates are compared with lake level estimates for Laguna Potrok Aike (LPA) from sediments. Relative to pre-industrial conditions (i.e. 1550–1850), which show extraordinarily high lake levels, the proxy-based reconstructed lake levels during the MH are lower. The downscaled simulated circulation differences indicate higher LPA precipitation during the MH from March to August, higher annual means, and reduced precipitation from September to February. Thus the reconstructed lower LPA lake levels can not be explained solely by the simulated precipitation changes. Possible reasons for this discrepancy are discussed. Based on proxy data from southern South America hypotheses have also been proposed on the latitudinal position of the southern hemispheric westerlies (SHWs). In agreement with some of these hypotheses our simulations show an increased seasonal cycle of the latitudinal position of the SHWs during the MH, which can be explained by the orbital forcing. The simulations also show stronger SHWs over southern Patagonia during austral summer and weaker SHWs during winter. The downscaling model associates weaker SHWs with increased precipitation in the LPA region. However, this relationship is only moderate, and therefore the downscaling model does not support the assumption of a strong link between mean SHWs and precipitation over south-eastern Patagonia, which is the basis of many proxy-based hypotheses about the SHWs.  相似文献   

Measurement of Ambient,Interstitial, and Residual Aerosol Particles on a Mountaintop Site in Central Sweden using an Aerosol Mass Spectrometer and a CVI     

Frank Drewnick  Johannes Schneider  Silke S. Hings  Nele Hock  Kevin Noone  Admir Targino  Silke Weimer  Stephan Borrmann 《Journal of Atmospheric Chemistry》2007,56(1):1-20

The Aerodyne aerosol mass spectrometer (Q-AMS) was coupled with a counterflow virtual impactor (CVI) for the first time to measure cloud droplet residuals of warm tropospheric clouds on Mt. Åreskutan in central Sweden in July 2003. Operating the CVI in different operational modes generated mass concentration and species-resolved mass distribution data for non-refractory species of the ambient, interstitial, and residual aerosol. The ambient aerosol measurements revealed that the aerosol at the site was mainly influenced by long-range transport and regional photochemical generation of nitrate and organic aerosol components. Four different major air masses were identified for the time interval of the experiment. While two air masses that approached the site from northeastern Europe via Finland showed very similar aerosol composition, the other two air masses from polar regions and the British Islands had a significantly different composition. During cloud events the larger aerosol particles were found to be activated into cloud droplets. On a mass basis the activation cut-off diameter was approximately 150 nm for nitrate and organics dominated particles and 200 nm for sulfate dominated particles. Generally nitrate and organics were found to be activated into cloud droplets with higher efficiency than sulfate. While a significant fraction of the nitrate in ambient particles was organic nitrates or nitrogen-containing organic species, the nitrate found in the cloud droplet residuals was mainly ammonium nitrate. After passage of clouds the ambient aerosol size distribution had shifted to smaller particle sizes due to the predominantly activation of larger aerosol particles without a significant change in the relative composition of the ambient aerosol.  相似文献   

Quantifying the impact of chemicals on stable carbon and oxygen isotope values of raw pollen     

Carolina Müller  Julian Hennig  Frank Riedel  Gerhard Helle 《第四纪科学杂志》2021,36(3):441-449

Purification protocols to extract pollen from lake sediments contain chemicals that alter the carbon and oxygen pollen-isotope values according to pollen characteristics and family affiliation. Modern (raw) pollen of broad-leaved (Alnus glutinosa, Betula pendula, Carpinus betulus, Corylus avellana, Fagus sylvatica and Quercus robur) and coniferous tree species (Picea abies and Pinus sylvestris) were treated with potassium hydroxide (KOH), hydrofluoric acid (HF), sodium hypochlorite (NaClO) and sulphuric acid (H₂SO₄) to test the impact on δ¹³C_pollen and δ¹⁸O_pollen and assess the applicability in purification protocols. Pollen of broad-leaved and coniferous trees reacted differently to chemical exposure, but response patterns are generally alike. Alterations of δ¹³C_pollen values vary between + 1.0‰ (B. pendula, NaClO-treatment) and −5.0‰ (P. sylvestris, H₂SO₄-treatment). The δ¹³C_pollen values of raw and chemically treated samples seem to be related after treatments with KOH, NaClO and HF, whereas the application of H₂SO₄ led to inconsistent changes among species. The impact of chemicals on δ¹⁸O_pollen are more diverse and offsets range between +1.1‰ (C. avellana, NaClO-treatment) and −17.9‰ (P. sylvestris, H₂SO₄-treatment). In general, the use of isotope-altering chemicals in purification protocols should be brought to a minimum, but the application of KOH and NaClO seems mostly unproblematic before δ¹³C_pollen and δ¹⁸O_pollen analysis.  相似文献