Denitrification capacity in a subterranean estuary below a Rhode Island fringing salt marsh     

Kelly Addy  Arthur Gold  Barbara Nowicki  James McKenna  Mark Stolt  Peter Groffman 《Estuaries and Coasts》2005,28(6):896-908

Coastal waters are severely threatened by nitrogen (N) loading from direct groundwater discharge. The subterranean estuary, the mixing zone of fresh groundwater and sea water in a coastal aquifer, has a high potential to remove substantial N. A network of piezometers was used to characterize the denitrification capacity and groundwater flow paths in the subterranean estuary below a Rhode Island fringing salt marsh.¹⁵N-enriched nitrate was injected into the subterranean estuary (in situ push-pull method) to evaluate the denitrification capacity of the saturated zone at multiple depths (125–300 cm) below different zones (upland-marsh transition zone, high marsh, and low marsh). From the upland to low marsh, the water table became shallower, groundwater dissolved oxygen decreased, and groundwater pH, soil organic carbon, and total root biomass increased. As groundwater approached the high and low marsh, the hydraulic gradient increased and deep groundwater upwelled. In the warm season (groundwater temperature >12 °C), elevated groundwater denitrification capacity within each zone was observed. The warm season low marsh groundwater denitrification capacity was significantly higher than all other zones and depths. In the cool season (groundwater temperature <10.5 °C), elevated groundwater denitrification capacity was only found in the low marsh. Additions of dissolved organic carbon did not alter groundwater denitrification capacity suggesting that an alternative electron donor, possibly transported by tidal inundation from the root zone, may be limiting. Combining flow paths with denitrification capacity and saturated porewater residence time, we estimated that as much as 29–60 mg N could be removed from 11 of water flowing through the subterranean estuary below the low marsh, arguing for the significance of subterranean estuaries in annual watershed scale N budgets.  相似文献   

Mechanism of loading on plates due to explosive detonation     

W. L. Fourney  U. Leiste  R. Bonenberger  D. J. Goodings 《Fragblast: International Journal for Blasting and Fragmentation》2005,9(4):205-217

This paper investigates the various mechanisms and parameters that are responsible for delivering impulse to a vehicle that is unfortunate enough to detonate a buried mine. Small scale tests are used to examine the effects of air blast or ejected sand in imparting impulse to a plate that is located above the surface of the saturated soil that contains the explosive. Parameters such as confinement, stand off distance, depth of burial of the explosive, density of the soil, and saturation level of the soil are also examined.  相似文献   

Calculation of the UV-visible spectra and the stability of Mo and Re oxysulfides in aqueous solution     

J.A. Tossell 《Geochimica et cosmochimica acta》2005,69(10):2497-2503

Erickson and Helz (2000) established that molybdate, MoO₄⁻², is quickly and completely transformed to thiomolybdate, MoS₄⁻², by reaction with sulfide. They monitored the equilibria and kinetics of this process by measuring the UV-visible spectra of solutions containing the different oxythiomolybdate species. There is interest in the analogous reactions for the ReO₄⁻ species but little experimental data. We have therefore calculated quantum-chemically the equilibrium constants in solution for the sulfidation reactions of both MoO₄⁻² and ReO₄⁻, as well as recalculating their UV-visible charge-transfer spectra. Calculations using configuration interaction singles and time-dependent hybrid Hartree-Fock density functional methods give good absolute values and trends in UV-vis energies for both series. For MoO₄⁻² the calculated equilibrium constants for the various sulfidation steps match reasonably well against the experimental values (within two log K units). For the ReO₄⁻ sulfidation reaction the first two steps are considerably less favorable than for MoO₄⁻², suggesting that the “geochemical switch” of Erickson and Helz, a rapid transformation of oxyanion to thioanion highly dependent on sulfide concentration, will be less effective in the Re case. However, both our calculations and experiment indicate that ReO₄⁻ and ReS₄⁻ are both easier to reduce than their Mo analogs, so that reduction of these Re(VII) species will be the preferred mechanism for their removal from seawater. A previous suggestion that the neutral species MoO₄H₂ is actually the hydrated octahedral Mo(OH)₆ species is found to be incorrect, but the MoO₃(OH₂)₃ species, a highly distorted six-coordinate complex, is almost competitive in energy with MoO₄H₂ plus two H₂O.  相似文献   

Kimberlite petrogenesis: Insights from clinopyroxene-melt partitioning experiments at 6 GPa in the CaO-MgO-Al₂O₃-SiO₂-CO₂ system     

Shantanu Keshav  Alexandre Corgne  Michael Bizimis  Yingwei Fei 《Geochimica et cosmochimica acta》2005,69(11):2829-2845

In this experimental study, we examine the mineral-melt partitioning of major and trace elements between clinopyroxene and CO₂-rich kimberlitic melts at a pressure of 6 GPa and temperatures of 1410°C and 1430°C. The melts produced contain ∼ 28 wt% dissolved CO₂, and are saturated with olivine and clinopyroxene. To assess the effects of temperature, crystal and melt compositions on trace element partitioning, experiments were performed in the model CaO-MgO-Al₂O₃-SiO₂-CO₂ system. Our results reveal that all the elements studied, except Al, Mg, Si, and Ga, are incompatible in clinopyroxene. Partition coefficients show a considerable range in magnitude, from ∼ 10⁻³ for D_U and D_Ba to ∼ 2.5 for D_Si. The two experimental runs show similar overall partitioning patterns with the D values being lower at 1430°C. Rare earth elements display a wide range of partition coefficients, D_La (0.012-0.026) being approximately one order of magnitude lower than D_Lu (0.18-0.23). Partition coefficients for the 2+ and 3+ cations entering the M2-site exhibit a near-parabolic dependence on radius of the incorporated cations as predicted from the lattice strain model. This underlines the contribution made by the crystal structure toward controlling the distribution of trace elements. Using data obtained in this study combined with that in the published literature, we also discuss the effects that other important parameters, namely, melt composition, pressure, and temperature, could have on partitioning.Our partition coefficients have been used to model the generation of the Group I (GI) kimberlites from South Africa. The numerical modeling shows that kimberlitic melts can be produced by ∼0.5% melting of a MORB-type depleted source that has been enriched by small-degree melts originating from a similar depleted source. This result suggests that the source of GI kimberlites may be located at the lithosphere-asthenosphere transition. Percolation of small degree melts from the asthenosphere would essentially create a metasomatic horizon near the bottom of the non-convecting sublithospheric mantle. Accumulation of such small degree melts together with the presence of volatiles and conductive heating would trigger melting of the ambient mantle and subsequently lead to eruption of kimberlitic melts. Additionally, our model shows that the GI source can be generated by metasomatism of a 2 Ga old MORB source ca. 1 Ga ago. Assuming that MORB-type mantle is the most depleted source of magmas on earth, then this is the oldest age at which the GI source could have existed. However, this age most likely reflects the average age of a series of metasomatic events than that of a single event.  相似文献   

Lithium isotopes in the system Qz-Ms-fluid:An experimental study     

Stephen J. Lynton  Richard J. Walker  Philip A. Candela 《Geochimica et cosmochimica acta》2005,69(13):3337-3347

The fractionation of lithium isotopes among quartz, muscovite, and a chloride-bearing aqueous fluid has been investigated experimentally at 400°-500°C and 50-100 MPa. Experiments were performed for 15-60 days in cold seal vessels with natural mineral specimens. Lithium was introduced primarily through the fluid, which also contained KCl and HCl. In most runs, the fluid was prepared with the L-SVEC standard (δ⁷Li = 0) and was 1 M in total chloride with K/Li/H = 100/10/1. In two experiments, a ⁶Li spike was employed. The experiments demonstrate that quartz and muscovite are susceptible to pronounced, rapid shifts in Li isotopic composition by diffusion through interaction with a Li-bearing fluid, particularly at 500°C. At 500°C, fractionation factors were determined to be Δ_{quartz-aqueous} ≅ +8 to + 12‰ and Δ_{muscovite-aqueous} ≅ +18 to + 20‰. An intermineral fractionation factor is given by Δ_{muscovite-quartz} ≈ +9‰. At 400°C, the results suggest Δ_{quartz-aqueous} ≈ +4 to + 6‰. The study provides evidence of systematic fractionation in lithium isotopes at the temperatures of some magmatic processes, such as those associated with porphyry-type ore systems and pegmatites.  相似文献   

Gold partitioning in melt-vapor-brine systems   总被引：5，自引：0，他引：5  

Adam C. Simon  Mark R. Frank  Philip A. Candela  Christoph A. Heinrich 《Geochimica et cosmochimica acta》2005,69(13):3321-3335

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.  相似文献   

Planetesimal sulfate and aqueous alteration in CM and CI carbonaceous chondrites     

S.A. Airieau  J. Farquhar  L.A. Leshin  E. Young 《Geochimica et cosmochimica acta》2005,69(16):4167-4172

Water-soluble sulfate salts extracted from six CM chondrites have oxygen isotope compositions that are consistent with an extraterrestrial origin. The Δ¹⁷O of sulfate are correlated with previously reported whole rock δ¹⁸O and with an index of meteorite alteration, and may display a correlation with the date of the fall. The enrichments and depletions for Δ¹⁷O of water-soluble sulfate from the CM chondrites relative to the terrestrial mass dependent fractionation line are consistent with sulfate formation in a rock dominated asteroidal environment, and from aqueous fluids that had undergone relatively low amounts of oxygen isotope exchange and little reaction with anhydrous components of the meteorites. It is unresolved how the oxidation of sulfide to sulfate can be reconciled with the inferred low oxidation state during the extraterrestrial alteration process. Oxygen isotope data for two CI chondrites, Orgueil and Ivuna, as well as the ungrouped C2 chondrite Essebi are indistinguishable from sulfate of terrestrial origin and may be terrestrial weathering products, consistent with previous assertions. Our oxygen isotope data, however, can not rule out a preterrestrial origin either.  相似文献   

Ab initio molecular orbital calculations for boron isotope fractionations on boric acids and borates   总被引：1，自引：0，他引：1  

Yun Liu  John A. Tossell 《Geochimica et cosmochimica acta》2005,69(16):3995-4006

Ab initio quantum chemistry calculations have been performed on the isotopic exchange reaction between B(OH)₃ and B(OH)₄⁻. Several calculation methods have been carefully compared and evaluated. The “water-droplet” method is chosen to investigate this isotope exchange reaction using cluster models with up to 34 water molecules surrounding the solute. HF/6-31G* level calculations coupled with a 0.920 scaling factor are used for the frequency calculations. A larger K value (1.027) is obtained from this study compared to the commonly used 1.0194 (Kakihana et al., 1977).The fractionations for several boric acid polymers and boron minerals are also studied. Our results suggest that assuming the BO₄ bonding in B(OH)₄⁻ is identical to that in borosilicates is wrong. Tetrahedral boron in silicates has a significantly smaller reduced isotopic partition function ratio (RPFR) and hence will be much isotopically lighter than in B(OH)₄⁻.The new theoretical curve of pH vs. δ¹¹B composition of B(OH)₄⁻ using our calculated 1.027 can be used to predict pH values for equilibrium cases such as incorporation into inorganic calcite. We also find that the shape of this curve is very sensitive to both K and pK_a value, giving the possibility of also predicting salinity from the different shapes of the curve.  相似文献   

Boric acid, “carbonic” acid, and N-containing oxyacids in aqueous solution: Ab initio studies of structure, pK_a, NMR shifts, and isotopic fractionations     

J.A. Tossell 《Geochimica et cosmochimica acta》2005,69(24):5647-5658

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Holocene glacier history of Bjørnbreen and climatic reconstruction in central Jotunheimen,Norway, based on proximal glaciofluvial stream-bank mires     

《Quaternary Science Reviews》2005,24(1-2):67-90

Holocene variations of Bjørnbreen, Smørstabbtinden massif, west-central Jotunheimen are reconstructed from the lithostratigraphy of two alpine stream-bank mires flooded episodically by meltwater. The approach uses multiple sedimentological indicators (weight loss-on-ignition, mean grain size, grain-size fractions, bulk density, moisture content and magnetic susceptibility), an a priori model of overbank deposition of suspended glaciofluvial sediments, a detailed chronology based on 56 radiocarbon dates, and a Little Ice Age sedimentological analogue. Rapid, late-Preboreal deglaciation was indicated by immigration of Betula pubescens by 9700 cal. BP. An interval of at least 3000 years in the early Holocene when glaciers were absent was interrupted by two abrupt episodes of glacier expansion around the time of the Finse Event, the first at ca 8270–7900 cal. BP (Bjørnbreen I Event) and the second at ca 7770–7540 cal. BP (Bjørnbreen II Event). Neoglaciation began shortly before ca 5730 cal. BP with gradual build-up to the maximum of the Bjørnbreen III Event at ca 4420 cal. BP. Later maxima occurred at ca 2750 cal. BP (Bjørnbreen IV Event) and at 1300, 1260, 1060 and 790 cal. BP (all within the Bjørnbreen V Event). Glaciers were smaller than today and possibly melted away on several occasions in the late Holocene (ca 3950, 1410 and 750 cal. BP). Minor maxima also occurred at ca 660 and 540 cal. BP, within the late Mediaeval Warm Period and the early Little Ice Age, respectively. The Little Ice Age maximum was dated to 213±25 BP (ca 205 cal. BP). The relative magnitudes of the main glacier maxima were determined: Erdalen Event>Little Ice Age Event (Bjørnbreen VI)>Bjørnbreen I (Finse Event) ≈ Bjørnbreen II>Bjørnbreen V⩾Bjørnbreen IV>Bjørnbreen III. These episodic events of varying magnitude and abruptness were used in conjunction with an independent summer-temperature proxy to reconstruct variations in equilibrium-line altitude (ELA) and a Holocene record of winter precipitation. Since the Preboreal, ELA varied within a range of about 390 m, and winter precipitation ranged between 40 and 160% of modern values. Winter precipitation variations appear to have been the main cause of these century- to millennial-scale Holocene glacier variations.  相似文献