Oxidation of pyrite during extraction of carbonate associated sulfate     

Pedro J. Marenco  Frank A. Corsetti  Douglas E. Hammond  Alan J. Kaufman  David J. Bottjer 《Chemical Geology》2008,247(1-2):124-132

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.  相似文献   

Integrated chronostratigraphy of Proterozoic-Cambrian boundary beds in the western Anabar region, northern Siberia   总被引：2，自引：0，他引：2  

Kaufman AJ  Knoll AH  Semikhatov MA  Grotzinger JP  Jacobsen SB  Adams W 《Geological magazine》1996,133(5):509-533

Carbonate-rich sedimentary rocks of the western Anabar region, northern Siberia, preserve an exceptional record of evolutionary and biogeochemical events near the Proterozoic/Cambrian boundary. Sedimentologically, the boundary succession can be divided into three sequences representing successive episodes of late transgressive to early highstand deposition; four parasequences are recognized in the sequence corresponding lithostratigraphically to the Manykal Formation. Small shelly fossils are abundant and include many taxa that also occur in standard sections of southeastern Siberia. Despite this coincidence of faunal elements, biostratigraphic correlations between the two regions have been controversial because numerous species that first appear at or immediately above the basal Tommotian boundary in southeastern sections have first appearances scattered through more than thirty metres of section in the western Anabar. Carbon- and Sr-isotopic data on petrographically and geochemically screened samples collected at one- to two-metre intervals in a section along the Kotuikan River, favour correlation of the Staraya Reckha Formation and most of the overlying Manykai Formation with sub-Tommotian carbonates in southeastern Siberia. In contrast, isotopic data suggest that the uppermost Manykai Formation and the basal 26 m of the unconformably overlying Medvezhya Formation may have no equivalent in the southeast; they appear to provide a sedimentary and palaeontological record of an evolutionarily significant time interval represented in southeastern Siberia only by the sub-Tommotian unconformity. Correlations with radiometrically dated horizons in the Olenek and Kharaulakh regions of northern Siberia suggest that this interval lasted approximately three to six million years, during which essentially all 'basal Tommotian' small shelly fossils evolved.  相似文献   

Photochemistry and Vertical Transport in Io's Atmosphere and Ionosphere     

Michael E. Summers  Darrell F. Strobel 《Icarus》1996,120(2):290-316

We present an updated model for the photochemistry of Io's atmosphere and ionosphere and use this model to investigate the sensitivity of the chemical structure to vertical transport rates. SO₂is assumed to be the dominant atmospheric gas, with minor molecular sodium species such as Na₂S or Na₂O released by sputtering or venting from the surface. Photochemical products include SO, O₂, S, O, Na, NaO, NaS, and Na₂. We consider both “thick” and “thin” SO₂atmospheres that encompass the range allowed by recent HST and millimeter-wave observations, and evaluate the possibility that O₂and/or SO may be significant minor dayside constituents and therefore likely dominant nightside gases. The fast reaction between S and O₂limits the column abundance of O₂to ∼10⁴less than that calculated by Kumar (J. Geophys. Res.87, 1677–1684, 1982; 89(A9), 7399–7406, 1984) for a pure sulfur/oxygen atmosphere. If a significant source of NaO₂or Na₂O were supplied by the surface and mixed rapidly upward, then oxygen liberated in the chemical reactions which also liberate free Na would provide an additional source of O₂. Fast eddy mixing will enhance the transport of molecular sodium species to the exobase, in addition to increasing the vertical transport rate of ions. Ions produced in the atmosphere will be accelerated by the reduced corotation electric field penetrating the atmosphere. These ions experience collisions with the neutral gas, leading to enhanced vertical ion diffusion. The dominant ion, Na⁺, is lost primarily by charge exchange with Na₂O and/or Na₂S in the lower atmosphere and by diffusion through the ionopause in the upper atmosphere. The atmospheric column abundance of SO, O₂, and the upper atmosphere escape rates of Na, S, O, and molecular sodium species are all strong functions of the eddy mixing rate. Most atmospheric escape, including that of molecular sodium species, probably occurs from the low density “background” SO₂atmosphere, while a localized high density “volcanic” SO₂atmosphere can yield an ionosphere consistent with that detected by the Pioneer 10 spacecraft.  相似文献   

Integrated chemostratigraphy and biostratigraphy of the Windermere Supergroup, northwestern Canada: implications for Neoproterozoic correlations and the early evolution of animals     

Narbonne GM  Kaufman AJ  Knoll AH 《Geological Society of America bulletin》1994,106(10):1281-1292

The thick, richly fossiliferous succession of the upper Windermere Supergroup, Mackenzie Mountains, northwestern Canada, provides a test of integrated biostratigraphic and chemostratigraphic frameworks in terminal Proterozoic correlation. The C- and Sr-isotopic abundances of lower Keele Formation carbonates approximate those for other pre-Varanger samples, confirming that the simple disc-like fossils of the underlying Twitya Formation predate all known diverse Ediacaran faunas. "Tepee" and Sheepbed carbonates record strong post-glacial isotopic excursions; in contrast, delta13C values for Gametrail through Risky carbonates vary only within the narrow range of about +l% to +2%. A second negative excursion occurs in Ingta Formation carbonates that immediately underlie the paleontologically determined Precambrian-Cambrian boundary. The upper Windermere profile as a whole compares closely with curves determined for other terminal Proterozoic successions. The lowermost diverse Ediacaran assemblages in the Sheepbed Formation correlate chemostratigraphically with the oldest fauna in Namibia, but the two assemblages differ in taxonomic composition. Blueflower assemblages correlate both chemostratigraphically and taxonomically with faunas from Australia, China, Siberia, and elsewhere. Increasing data support the hypothesis that paleontological and geochemical data together provide a reliable means of correlating terminal Proterozoic sedimentary rocks throughout the world.  相似文献   

Photochemistry of nitrogen in the Martian atmosphere     

Darrell F. Strobel  Michael B. McElroy 《Icarus》1977,30(1):26-41

Models are developed for the photochemistry of a CO₂H₂ON₂ atmosphere on Mars and estimates are given for the concentrations of N, NO, NO₂, NO₃, N₂O₅, HNO₂, HNO₃, and N₂O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO₂ of order 10^?8. Deposition rates for nitrite and nitrate minerals could be as large as 3× 10⁵ N equivalent atoms cm^?2 sec^?1 under present conditions and may have been higher in the past.  相似文献   

Speciation of volatile arsenic at geothermal features in Yellowstone National Park   总被引：1，自引：0，他引：1  

Britta Planer-Friedrich  Corinne Lehr  Jörg Matschullat  Darrell Kirk Nordstrom 《Geochimica et cosmochimica acta》2006,70(10):2480-2491

Geothermal features in the Yellowstone National Park contain up to several milligram per liter of aqueous arsenic. Part of this arsenic is volatilized and released into the atmosphere. Total volatile arsenic concentrations of 0.5-200 mg/m³ at the surface of the hot springs were found to exceed the previously assumed nanogram per cubic meter range of background concentrations by orders of magnitude. Speciation of the volatile arsenic was performed using solid-phase micro-extraction fibers with analysis by GC-MS. The arsenic species most frequently identified in the samples is (CH₃)₂AsCl, followed by (CH₃)₃As, (CH₃)₂AsSCH₃, and CH₃AsCl₂ in decreasing order of frequency. This report contains the first documented occurrence of chloro- and thioarsines in a natural environment. Toxicity, mobility, and degradation products are unknown.  相似文献   

Late Quaternary Spring-Fed Deposits of the Grand Canyon and Their Implication for Deep Lava-Dammed Lakes     

Darrell S. Kaufman  Gary O'Brien  Jim I. Mead  Jordon Bright  Paul Umhoefer 《Quaternary Research》2002,58(3):329

One of the most intriguing episodes in the Quaternary evolution of the Grand Canyon of the Colorado River, Arizona, was the development of vast lakes that are thought to have backed up behind lava erupted into the gorge. Stratigraphic evidence for these deep lava-dammed lakes is expectedly sparse. Possible lacustrine deposits at six areas in the eastern canyon yielded no compelling evidence for sediment deposited in a deep lake. At two of the sites the sediment was associated with late Quaternary spring-fed pools and marshes. Water-lain silt and sand at lower Havasu Creek was deposited 3000 cal yr ago. The deposit contains an ostracode assemblage similar to that living in the modern travertine-dammed pools adjacent to the outcrop. The second deposit, at Lees Ferry, formed in a spring-fed marsh 43,000 cal yr ago, as determined by ¹⁴C and amino acid geochronology. It contains abundant ostracode and mollusk fossils, the richest assemblages reported from the Grand Canyon to date. Our interpretation of these sediments as spring-fed deposits, and their relative youth, provides an alternative to the conventional view that deposits like these were formed in deep lava-dammed lakes that filled the Grand Canyon.  相似文献   

Paleoclimate reconstruction based on the timing of speleothem growth and oxygen and carbon isotope composition in a cave located in the rain shadow in Israel     

Anton VaksMiryam Bar-Matthews  Avner AyalonBettina Schilman  Mabs GilmourChris J Hawkesworth  Amos FrumkinAaron Kaufman  Alan Matthews 《Quaternary Research》2003,59(2):182-193

High-resolution ²³⁰Th/²³⁴U ages and δ¹⁸O and δ¹³C compositions of speleothems in Ma’ale Efrayim Cave located to the east of the central mountain ridge of Israel enable us to examine the nature of the rain shadow aridity during glacial and interglacial intervals. Speleothem growth occurred during marine glacial isotopic periods, with no growth during the two last marine isotope interglacial intervals and during the peak of the Last Glacial Maximum. This contrasts with speleothem growth in caves located on the western flank of the central mountain ridge, in the Eastern Mediterranean semiarid climatic zone, which continued throughout the last 240,000 yr. Thus, during glacial periods water reached both sides of the central mountain ridge. A comparison of the present-day rain and cave water isotopic compositions and amounts at the Ma’ale Efrayim Cave site with those on the western flank shows that evaporation and higher temperatures on the eastern flank are major influences on isotopic composition and the lack of rainfall. The δ¹⁸O and δ¹³C profiles of the speleothems deposited between 67,000 and 25,000 yr B.P. match the general trends of the isotopic profiles of Soreq Cave speleothems, suggesting a similar source (eastern Mediterranean Sea) and similar climatic conditions. Thus, during glacial periods the desert boundary effectively migrated further south or east from its present-day location on the eastern flank, whereas interglacial periods appear to have been similar to the present, with the desert boundary at the same position. The decrease in overall temperature and a consequent reduction in the evaporation to precipitation ratios on the eastern flank are viewed as the major factors controlling the decay of the rain shadow effect during glacial periods.  相似文献   

Structure and thermal regime beneath the South Pole region, East Antarctica, from magnetotelluric measurements     

Philip E. Wannamaker  John A. Stodt  Louise Pellerin  Steven L. Olsen  Darrell B. Hall 《Geophysical Journal International》2004,157(1):36-54

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Has the Largest Field Been Discovered Yet? PETRIMES and GRASP 25 Years Later     

Gordon M. Kaufman  Ray Faith  John H. Schuenemeyer 《Mathematical Geosciences》2016,48(8):873-890

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