Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS   总被引：4，自引：0，他引：4  

Paul R. Craddock  Olivier J. Rouxel  Lary A. Ball  Wolfgang Bach   《Chemical Geology》2008,253(3-4):102-113

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.  相似文献   

Determining effective wellbore permeability from a field pressure test: a numerical analysis of detection limits     

Sarah E. Gasda  Jan M. Nordbotten  Michael A. Celia 《Environmental Geology》2008,54(6):1207-1215

We propose a simple pressure test that can be used in the field to determine the effective permeability of existing wellbores. Such tests are motivated by the need to understand and quantify leakage risks associated with geological storage of CO₂ in mature sedimentary basins. If CO₂ is injected into a deep geological formation, and the resulting CO₂ plume encounters a wellbore, leakage may occur through various pathways in the “disturbed zone” surrounding the well casing. The effective permeability of this composite zone, on the outside of the well casing, is an important parameter for models of leakage. However, the data that exist on this key parameter do not exist in the open literature, and therefore specific field tests need to be done in order to reduce the uncertainty inherent in the leakage estimates. The test designed and analyzed herein is designed to measure effective wellbore permeability within a low-permeability caprock, bounded above and below by permeable reservoirs, by pressurizing the reservoir below and measuring the response in the reservoir above. Alternatively, a modified test can be performed within the caprock without directly contacting the reservoirs above and below. We use numerical simulation to relate pressure response to effective well permeability and then evaluate the range of detection of the effective permeability based on instrument measurement error and limits on fracture pressure. These results can guide field experiments associated with site characterization and leakage analysis.  相似文献   

Numerical modeling assessment of three-gate structures for capturing contaminated groundwater     

Paul F. Hudak 《Environmental Geology》2008,55(6):1311-1317

This modeling study evaluated the capability of alternative funnel-and-gate structures with three gates for capturing contaminated groundwater in a hypothetical unconfined aquifer. Simulated interceptor structures were linear and 45 m wide, consisting of three gates and two funnels (walls). One gate occupied the center and two gates occupied the ends of the interceptor structures. The structures, positioned perpendicular to regional groundwater flow, traversed the entire thickness of the aquifer. A total of four structures were evaluated (numbers designate widths of end, center, and end gates, respectively, in meters): 3-3-3, 2-5-2, 1-7-1, and 4-1-4. Particle tracking and zonal water budgets identified shapes of capture zones and discharge patterns for each interceptor structure. A mass transport model, accounting for advection and hydrodynamic dispersion, tested the capability of each structure for capturing a contaminant plume. Results suggest that: time-dependent capture zones underestimate the amount of time to capture a contaminant plume, wide center gates facilitate plume capture, and wide end gates facilitate lateral containment of contaminants. Of the structures simulated, the 2-5-2 configuration was relatively efficient at processing and containing the simulated contaminant plume.  相似文献   

Late Palaeozoic hydrocarbon migration through the Clair field, West of Shetland, UK Atlantic margin     

Darren F. Mark  Paul F. Green  John Parnell  Simon P. Kelley  Martin R. Lee  Sarah C. Sherlock 《Geochimica et cosmochimica acta》2008,72(10):2510-2533

Geochemical analysis of bitumen- and hydrocarbon-bearing fluid inclusions from the Devonian-Carboniferous Clair field indicates that the reservoirs contain a mixture of oils from different marine and lacustrine sources. Reconstruction of the Clair field oil-charge history using fluid inclusion petrography show that oil-charging occurred at times of K-feldspar, quartz and calcite cementation. Temperature–composition–time data yielded from the integration of fluid inclusion microthermometry with high-resolution Ar–Ar dating, date hydrocarbon-bearing K-feldspar overgrowths at 247 ± 3.3 Ma. These data show that in order for oil to be trapped within primary fluid inclusions in K-feldspar overgrowths, hydrocarbon migration throughout the UK Atlantic margin must have been taking place during the Late Palaeozoic and as such, current industry oil-play models based solely on oil charging from Jurassic-Cretaceous marine sources are clearly incomplete and need revision. Apatite fission track analysis and vitrinite reflectance data were used to reconstruct thermal burial histories and assess potential oil generation from Middle Devonian lacustrine source rocks. Thermal history data from wells along The Rona Ridge adjacent to the Clair field show that the Palaeozoic section was heated to greater than 100 °C at some time between 270 and 230 Ma, confirming that Devonian source rocks were mature and expelling oil during the Late Palaeozoic at the time that authigenic K-feldspar overgrowths were growing in the Clair field.  相似文献   

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting   总被引：1，自引：0，他引：1  

Mauro Lo Cascio  Yan Liang  Nobumichi Shimizu  Paul C. Hess 《Contributions to Mineralogy and Petrology》2008,156(1):87-102

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  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   

Pressures of Crystallization of Icelandic Magmas   总被引：1，自引：0，他引：1  

Kelley  Daniel F.; Barton  Michael 《Journal of Petrology》2008,49(3):465-492

Iceland lies astride the Mid-Atlantic Ridge and was createdby seafloor spreading that began about 55 Ma. The crust is anomalouslythick (20–40 km), indicating higher melt productivityin the underlying mantle compared with normal ridge segmentsas a result of the presence of a mantle plume or upwelling centeredbeneath the northwestern edge of the Vatnajökull ice sheet.Seismic and volcanic activity is concentrated in 50 km wideneovolcanic or rift zones, which mark the subaerial Mid-AtlanticRidge, and in three flank zones. Geodetic and geophysical studiesprovide evidence for magma chambers located over a range ofdepths (1·5–21 km) in the crust, with shallow magmachambers beneath some volcanic centers (Katla, Grimsvötn,Eyjafjallajökull), and both shallow and deep chambers beneathothers (e.g. Krafla and Askja). We have compiled analyses ofbasalt glass with geochemical characteristics indicating crystallizationof ol–plag–cpx from 28 volcanic centers in the Western,Northern and Eastern rift zones as well as from the SouthernFlank Zone. Pressures of crystallization were calculated forthese glasses, and confirm that Icelandic magmas crystallizeover a wide range of pressures (0·001 to 1 GPa), equivalentto depths of 0–35 km. This range partly reflects crystallizationof melts en route to the surface, probably in dikes and conduits,after they leave intracrustal chambers. We find no evidencefor a shallow chamber beneath Katla, which probably indicatesthat the shallow chamber identified in other studies containssilica-rich magma rather than basalt. There is reasonably goodcorrelation between the depths of deep chambers (> 17 km)and geophysical estimates of Moho depth, indicating that magmaponds at the crust–mantle boundary. Shallow chambers (<7·1 km) are located in the upper crust, and probablyform at a level of neutral buoyancy. There are also discretechambers at intermediate depths (11 km beneath the rift zones),and there is strong evidence for cooling and crystallizing magmabodies or pockets throughout the middle and lower crust thatmight resemble a crystal mush. The results suggest that themiddle and lower crust is relatively hot and porous. It is suggestedthat crustal accretion occurs over a range of depths similarto those in recent models for accretionary processes at mid-oceanridges. The presence of multiple stacked chambers and hot, porouscrust suggests that magma evolution is complex and involvespolybaric crystallization, magma mixing, and assimilation. KEY WORDS: Iceland rift zones; cotectic crystallization; pressure; depth; magma chamber; volcanic glass  相似文献   

Global Correlations of Ocean Ridge Basalt Chemistry with Axial Depth: a New Perspective   总被引：4，自引：0，他引：4  

Niu  Yaoling; O'Hara  Michael J. 《Journal of Petrology》2008,49(4):633-664

The petrological parameters Na₈ and Fe₈, which are Na₂O andFeO contents in mid-ocean ridge basalt (MORB) melts correctedfor fractionation effects to MgO = 8 wt%, have been widely usedas indicators of the extent and pressure of mantle melting beneathocean ridges. We find that these parameters are unreliable.Fe₈ is used to compute the mantle solidus depth (P_o) and temperature(T_o), and it is the values and range of Fe₈ that have led tothe notion that mantle potential temperature variation of T_P= 250 K is required to explain the global ocean ridge systematics.This interpreted T_P = 250 K range applies to ocean ridges awayfrom ‘hotspots’. We find no convincing evidencethat calculated values for P_o, T_o, and T_P using Fe₈ have anysignificance. We correct for fractionation effect to Mg^# = 0·72,which reveals mostly signals of mantle processes because meltswith Mg^# = 0·72 are in equilibrium with mantle olivineof Fo_89·6 (vs evolved olivine of Fo_{88·1–79·6}in equilibrium with melts of Fe₈). To reveal first-order MORBchemical systematics as a function of ridge axial depth, weaverage out possible effects of spreading rate variation, local-scalemantle source heterogeneity, melting region geometry variation,and dynamic topography on regional and segment scales by usingactual sample depths, regardless of geographical location, withineach of 22 ridge depth intervals of 250 m on a global scale.These depth-interval averages give Fe₇₂ = 7·5–8·5,which would give T_P = 41 K (vs 250 K based on Fe₈) beneathglobal ocean ridges. The lack of Fe₇₂–Si₇₂ and Si₇₂–ridgedepth correlations provides no evidence that MORB melts preservepressure signatures as a function of ridge axial depth. We thusfind no convincing evidence for T_P > 50 K beneath globalocean ridges. The averages have also revealed significantcorrelations of MORB chemistry (e.g. Ti₇₂, Al₇₂, Fe₇₂,Mg₇₂, Ca₇₂, Na₇₂ and Ca₇₂/Al₇₂) with ridge axial depth. Thechemistry–depth correlation points to an intrinsic linkbetween the two. That is, the 5 km global ridge axial reliefand MORB chemistry both result from a common cause: subsolidusmantle compositional variation (vs T_P), which determines themineralogy, lithology and density variations that (1) isostaticallycompensate the 5 km ocean ridge relief and (2) determine thefirst-order MORB compositional variation on a global scale.A progressively more enriched (or less depleted) fertileperidotite source (i.e. high Al₂O₃ and Na₂O, and low CaO/Al₂O₃)beneath deep ridges ensures a greater amount of modal garnet(high Al₂O₃) and higher jadeite/diopside ratios in clinopyroxene(high Na₂O and Al₂O₃, and lower CaO), making a denser mantle,and thus deeper ridges. The dense fertile mantle beneath deepridges retards the rate and restricts the amplitude of the upwelling,reduces the rate and extent of decompression melting, givesway to conductive cooling to a deep level, forces melting tostop at such a deep level, leads to a short melting column,and thus produces less melt and probably a thin magmatic crustrelative to the less dense (more refractory) fertile mantlebeneath shallow ridges. Compositions of primitive MORB meltsresult from the combination of two different, but geneticallyrelated processes: (1) mantle source inheritance and (2) meltingprocess enhancement. The subsolidus mantle compositional variationneeded to explain MORB chemistry and ridge axial depth variationrequires a deep isostatic compensation depth, probably in thetransition zone. Therefore, although ocean ridges are of shalloworigin, their working is largely controlled by deep processesas well as the effect of plate spreading rate variation at shallowlevels. KEY WORDS: mid-ocean ridges; mantle melting; magma differentiation; petrogenesis; MORB chemistry variation; ridge depth variation; global correlations; mantle compositional variation; mantle source density variation; mantle potential temperature variation; isostatic compensation  相似文献   

Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks     

Garcia  Michael O.; Ito  Emi; Eiler  John M. 《Journal of Petrology》2008,49(4):757-769

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination  相似文献   

Characterization and cycling of atmospheric mercury along the central US Gulf Coast     

Mark A. Engle  Michael T. Tate  David P. Krabbenhoft  Allan Kolker  Mark L. Olson  Eric S. Edgerton  John F. DeWild  Ann K. McPherson 《Applied Geochemistry》2008

Concentrations of atmospheric Hg species, elemental Hg (Hg^°), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM_2.5) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m⁻³, 4.0 ± 7.5 pg m⁻³ and 2.7 ± 3.4 pg m⁻³, respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m⁻³), but not for Hg^° or Hg-PM_2.5. Elevated RGM concentrations (>25 pg m⁻³) in April and May of 2005 correlated with elevated average daytime O₃ concentrations (>55 ppbv) and high light intensity (>500 W m⁻²). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly (p < 0.05) with peaks in SO₂ concentration and corresponded to periods of high light intensity and lower average daytime O₃ concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg^° by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM.  相似文献