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   

Size scales over which ordinary chondrites and their parent asteroids are homogeneous in oxidation state and oxygen-isotopic composition   总被引：1，自引：0，他引：1  

Alan E. Rubin  Karen Ziegler 《Geochimica et cosmochimica acta》2008,72(3):948-958

Literature data demonstrate that on a global, asteroid-wide scale (plausibly on the order of 100 km), ordinary chondrites (OC) have heterogeneous oxidation states and O-isotopic compositions (represented, respectively, by the mean olivine Fa and bulk Δ¹⁷O compositions of equilibrated samples). Samples analyzed here include: (a) two H5 chondrite Antarctic finds (ALHA79046 and TIL 82415) that have the same cosmic-ray exposure age (7.6 Ma) and were probably within ∼1 km of each other when they were excavated from the H-chondrite parent body, (b) different individual stones from the Holbrook L/LL6 fall that were probably within ∼1 m of each other when their parent meteoroid penetrated the Earth’s atmosphere, and (c) drill cores from a large slab of the Estacado H6 find located within a few tens of centimeters of each other. Our results indicate that OC are heterogeneous in their bulk oxidation state and O-isotopic composition on 100-km-size scales, but homogeneous on meter-, decimeter- and centimeter-size scales. (On kilometer size scales, oxidation state is heterogeneous, but O isotopes appear to be homogeneous.) The asteroid-wide heterogeneity in oxidation state and O-isotopic composition was inherited from the solar nebula. The homogeneity on small size scales was probably caused in part by fluid-assisted metamorphism and mainly by impact-gardening processes (which are most effective at mixing target materials on scales of ?1 m).  相似文献   

Fast kimberlite ascent rates estimated from hydrogen diffusion profiles in xenolithic mantle olivines from southern Africa   总被引：4，自引：0，他引：4  

Anne H. Peslier  Alan B. Woodland 《Geochimica et cosmochimica acta》2008,72(11):2711-2722

Fourier transform infrared spectrometry (FTIR) analyses of olivines from peridotite xenoliths found in southern African kimberlites indicate 0 to 80 ppm H₂O concentrations. OH absorbance profiles across olivine grains show homogeneous H contents from core to edge for most samples. In one sample the olivines are H-free, while another has olivines characterized by lower H contents at the grain edges compared to the cores, indicating H loss during transport of the xenolith to the surface. Flat or near-flat H profiles place severe constraints on the duration of H loss from olivine grains, with implications for kimberlite magma ascent rates. Diffusion equations were used to estimate times of H loss of about 4 h for the sample with heterogeneous olivine H contents. Resulting kimberlite ascent rates are calculated to be 5-37 m s⁻¹ minimum, although these estimates are highly dependent on volatile contents and degassing behavior of the host kimberlite magma. Xenolithic olivines from alkali basalts generally have lower H contents and more pronounced H diffusion profiles than do those from kimberlites. This difference is likely caused by higher magma temperatures and lower ascent rates of alkali basalts compared to kimberlites.  相似文献   

A depleted, not ideally chondritic bulk Earth: The explosive-volcanic basalt loss hypothesis     

Paul H. Warren 《Geochimica et cosmochimica acta》2008,72(8):2217-2235

It has long been customary to assume that in the bulk composition of the Earth, all refractory-lithophile elements (including major oxides Al₂O₃ and CaO, all of the REE, and the heat-producing elements Th and U) occur in chondritic, bulk solar system, proportion to one another. Recently, however, Nd-isotopic studies (most notably Boyet M. and Carlson R. W. (2006) A new geochemical model for the Earth’s mantle inferred from ¹⁴⁶Sm-¹⁴²Nd systematics. Earth Planet. Sci. Lett.250, 254-268) have suggested that at least the outer portion of the planet features a Nd/Sm ratio depleted to ∼0.93 times the chondritic ratio. The primary reaction to this type of evidence has been to invoke a “hidden” reservoir of enriched matter, sequestered into the deepest mantle as a consequence of primordial differentiation. I propose a hypothesis that potentially explains the evidence for Nd/Sm depletion in a very different way. Among the handful of major types of differentiated asteroidal meteorites, two (ureilites and aubrites) are ultramafic restites so consistently devoid of plagioclase that meteoriticists were once mystified as to how all the complementary plagioclase-rich matter (basalt) was lost. The explanation appears to be basalt loss by graphite-fueled explosive volcanism on roughly 100-km sized planetesimals; with the dispersiveness of the process dramatically enhanced, relative to terrestrial experience, because the pyroclastic gases expand into vacuous space (Wilson L. and Keil K. (1991) Consequences of explosive eruptions on small Solar System bodies: the case of the missing basalts on the aubrite parent body. Earth Planet. Sci. Lett.104, 505-512). By analogy with lunar pyroclastic products, the typical size of pyroclastic melt/glass droplets under these circumstances will be roughly 0.1 mm. Once separated from an asteroidal or planetesimal gravitational field, droplets of this size will generally spiral toward the Sun, rather than reaccrete, because drag forces such the Poynting-Robertson effect quickly modify their orbits (the semimajor axis, in a typical scenario, is reduced by several hundred km during the first trip around the Sun). Assuming a similar process occurred on many of the Earth’s precursor planetesimals while they were still roughly 100 km in diameter, the net effect would be a depleted composition for the final Earth. I have modeled the process of trace-element depletion in the planetesimal mantles, assuming the partial melting was nonmodal and either batch or dynamic in terms of the melt-removal style. Assuming the process is moderately efficient, typical final-Earth Nd/Sm ratios are 0.93-0.96 times chondritic. Depletion is enhanced by a relatively low assumed residual porosity in batch-melting scenarios, but dampened by a relatively high value for “continuous” residue porosity in dynamic melting scenarios. Pigeonite in the source matter has a dampening effect on depletion. There are important side effects to the Nd/Sm depletion. The heat-producing elements, Th, U and K, might be severely depleted. The Eu/Eu^∗ ratio of the planet is unlikely to remain precisely chondritic. One of the most inevitable side effects, depletion of the Al/Ca ratio, is consistent with an otherwise puzzling aspect of the composition of the upper mantle. A perfectly undepleted composition for the bulk Earth is dubious.  相似文献   

The hydrochemistry of a semi-arid pan basin case study: Sua Pan,Makgadikgadi, Botswana     

Frank D. Eckardt  Robert G. Bryant  Graham McCulloch  Baruch Spiro  Warren W. Wood 《Applied Geochemistry》2008

This study presents results on the fluid and salt chemistry for the Makgadikgadi, a substantial continental basin in the semi-arid Kalahari. The aims of the study are to improve understanding of the hydrology of such a system and to identify the sources of the solutes and the controls on their cycling within pans. Sampling took place against the backdrop of unusually severe flooding as well as significant anthropogenic extraction of subsurface brines. This paper examines in particular the relationship between the chemistry of soil leachates, fresh stream water, salty lake water, surface salts and subsurface brines at Sua Pan, Botswana with the aim of improving the understanding of the system’s hydrology. Occasionally during the short wet season (December–March) surface water enters the saline environment and precipitates mostly calcite and halite, as well as dolomite and traces of other salts associated with the desiccation of the lake. The hypersaline subsurface brine (up to TDS 190,000 mg/L) is homogenous with minor variations due to pumping by BotAsh mine (Botswana Ash (Pty) Ltd.), which extracts 2400 m³ of brine/h from a depth of 38 m. Notable is the decrease in TDS as the pumping rate increases which may be indicative of subsurface recharge by less saline water. Isotope chemistry for Sr (⁸⁷Sr/⁸⁶Sr average 0.722087) and S (δ³⁴S average 34.35) suggests subsurface brines have been subject to a lithological contribution of undetermined origin. Recharge of the subsurface brine from surface water including the Nata River appears to be negligible.  相似文献   

Heat exchange between water and ice in the Arctic Ocean     

Robert Alan Lake 《Meteorology and Atmospheric Physics》1967,16(2-3):242-259

Summary The heat balance equation for the bottom surface of floating sea ice is evaluated on the basis of observations of ice temperature, water temperature, current velocity, and ablation or accretion of ice. Assuming equality of the eddy diffusivities for momentum, heat, and salt (average 24 cm² sec^–1) it is shown that the temperature gradient in the oceanic boundary layer is extremely small (averages between 2.10^–5 and 4.10^–4°C/meter) and difficult to measure directly. It is suggested that a large part of the heat transfer from the relatively warm Atlantic water to the arctic atmosphere may occur through open leads in the ice cover.

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Zusammenfassung Die Wärmebilanzgleichung für die Unterseite von schwimmendem Meereis wird an Hand von Beobachtungen der Eistemperatur, der Wassertemperatur, der Strömungsgeschwindigkeit und der Eisdickenänderung ausgewertet. Unter der Annahme gleicher Austauschkoeffizienten für Bewegungsgröße, Wärme und Salzgehalt (im Mittel 24 cm² sec^–1) ergibt sich für die ozeanische Grenzschicht ein außerordentlich kleiner Gradient der Wassertemperatur (durchschnittlich zwischen 2.10^–5 und 4.10^–4°C/Meter), der durch direkte Beobachtungen schwer nachzuweisen ist. Es ist zu vermuten, daß ein beträchtlicher Teil der Wärmeabgabe von der relativ warmen atlantischen Wassermasse an die arktische Atmosphäre durch Öffnungen in der Meereisdecke erfolgt.

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Résumé On établit l'équation du bilan thermique valable pour la surface inférieure de la glace marine dérivante. Pour ce faire, on se sert d'observations de la température de la glace, de celle de l'eau, de la vitesse du courant et des variations de l'épaisseur de la glace. En admettant que les coefficients d'échange sont les mêmes pour la quantité de mouvement, la chaleur et le taux de salinité (en moyenne 24 cm² sec^–1), il résulte pour la couche limite un gradient extrêmement faible de la température de l'eau (situé en moyenne entre 2·10^–5 et 4·10^–4°C/m); un tel gradient est difficile à prouver au moyen d'observations directes. On peut supposer qu'une partie importante de la chaleur transmise par l'eau relativement chaude de l'Atlantique à l'atmosphère arctique passe au travers des lacunes de la couche de glace recouvrant l'océan.

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With 4 Figures

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Contribution 141, Department of Atmospheric Sciences, University of Washington, Seattle. This is a thesis submitted by the author in partial fulfillment of the requirements for the degree of Master of Science.  相似文献   

The sea-surface microlayer of puget sound: Part I. Toxic effects on fish eggs and larvae     

John Hardy  Steven Kiesser  Liam Antrim  Alan Stubin  Richard Kocan  John Strand 《Marine environmental research》1987,23(4)

The sea surface is an important habitat for the developmental stages (eggs and larvae) of many fish and invertebrates; it is also a concentration point for anthropogenic contaminants entering the sea. Studies were conducted to determine the extent to which the sea surface of Puget Sound was toxic to the early life history stages of fish. Three urban bays with suspected contamination, a rural reference bay, and a Central Sound site were compared. Surface-dwelling eggs and organisms (zooneuston) were collected with a surface-skimming neuston net and their densities enumerated. Sand sole (Psettichthys melanostictus) embryos were exposed in the field and laboratory to the sea-surface microlayer. To develop a useful year-round approach to monitoring sea-surface toxicity, larval development of anchovies, kelp bass, and sea urchins was also evaluated as an indication of sea-surface microlayer toxicity.During the spawning season (February and March), urban boys in Puget Sound had lower concentrations of sand sole eggs and neustonic organisms on the sea surface than did the rural bayor Central Sound reference sites. Compared to the reference sites, laboratory exposure to surface microlayer samples collected from urban bay sites generally resulted in more chromsomal aberrations in developing sole embryos, reduced hatching success of sole larvae, and reduced growth in trout cell cultures. In situ hatching success of sole eggs was reduced by half or more in urban bays compared to reference sites.Toxicity was associated with visible surface slicks and, in urban bays, increased with increasing surface pressure (dynes cm⁻¹). Results to be reported separately (Part II) indicate that toxicity is strongly correlated with the presence of high concentrations of polycyclic aromatic hydrocarbons and metals in the sea-surface microlayer. The toxicity of SMIC samples was similar when evaluated by sole, anchovy, kelp bass, or sea urchin tests. A sea-surface monitoring program could use sea urchin embryos to evaluate site-specific sea-surface toxicity throughout the year.  相似文献   

A New Genus and Species of Rhynchonellid (Brachiopoda, Recent) from Submarine Caves in the Mediterranean Sea   总被引：1，自引：0，他引：1  

Alan  Logan Helmut  Zibrowius 《Marine Ecology》1994,15(1):77-88

Abstract. A new rhynchonellid brachiopod genus Tethyrhynchia , with type species Tethyrhynchia mediterranea n. sp., is described from specimens discovered in dark zones of submarine caves along the Mediterranean coast of France between Marseille and La Ciotat, and also at Zembra Island, off the Gulf of Tunis, Tunisia. Other brachiopods occurring with this diminutive rhynchonellid are also small and include the megathyridids Argyrotheca cistellula and Megathiris detruncata . This is the first recorded occurrence of a rhynchonellid from the Mediterranean Sea. The new form is apparently neotenous, in that the lophophore in adults never develops beyond the trocholophous stage. A new type of rhynchonellid crus, crescentic in profile and here named the lunifer type, is described. The new genus is assigned to the new family Tethyrhynchiidae , and comparisons are made with other extant rhynchonellid genera.  相似文献   

Glutathione S-transferase from an antarctic fish, Dissostichus mawsoni     

K.Cameron Falkner  Alan G. Clark 《Marine environmental research》1992,34(1-4)

Glutathione S-transferase activity was measured in the hepatic cytosol front Dissostichus mawsoni and Pagothenia borchgrevinki. Activity measures with 1-chloro-2,4-dinitrobenzene as substrate were 11·2 and 16·7 μmol/min/g tissue respectively. Little or no activity was detected when p-nitrobenzyl chloride or 3,4-dichloro-1-nitrobenzene were used as substrate. The hepatic glutathione S-transferases from D. mawsoni were partially purified using gel filtration and chromatofocusing. Three peaks of activity were resolved. The major isozyme (158-fold purification) eluting at pH7·1 appeared to be catalytically a homodimer. The isozyme was highly inhibited by triphenyltin chloride (IC₅₀ = 0·1 μ) while inhibition constants for Cibicron Blue 3GA, bromosulphophalein and hematin were 1·1, 20 and 34 μ respectively.  相似文献   

Direct determination of organic carbon in modern reef sediments and calcareous organisms after dissolution of carbonate     

Mark W. Sandstrom  Frank Tirendi  Alan Nott 《Marine Geology》1986,70(3-4):321-329

An improved method for the direct determination of organic carbon in calcareous marine sediments, organisms and particulate matter is described. Samples are dissolved in phosphoric acid to remove carbonates, purged with oxygen to remove CO₂, and the resulting acidic solution is analysed for total (dissolved and particulate) organic carbon. The method is rapid, involves minimal sample manipulation, and is both accurate (better than ± 2%) and precise (better than ± 0.2 mg organic carbon/g sediment). The method is especially suitable for modern carbonate sediments which have low levels of predominantly acid-soluble organic carbon.  相似文献