An absolute paleotemperature record from 10 to 6 Ka inferred from fluid inclusion D/H ratios of a stalagmite from Vancouver Island, British Columbia, Canada     

Ren Zhang  Henry P. Schwarcz 《Geochimica et cosmochimica acta》2008,72(4):1014-1026

By using continuous helium flow during the crushing of calcite speleothem samples, we are able to recover liberated inclusion waters without isotopic fractionation. A paleotemperature record for the Jacklah Jill Cave locality, Vancouver Island, BC, was obtained from a 30-cm tall stalagmite that grew 10.3-6.3 Ka ago, using δ¹⁸O values of the crushed calcite and of the inclusion water as inferred from its δD. It is found that the locality experienced mean annual temperature variations up to 11 °C over a 4-Ka period in the early Holocene. At the beginning of the period, local temperature quickly increased from a minimum of ∼1 °C to around 10 °C, but this early climate optimum, about 3 °C warmer than today, only lasted for ∼1200 years. About 8.6 Ka ago, temperature had declined to ∼7 °C, approximately the same as the modern cave temperature. Since then, the study area has experienced only minor temperature fluctuations, but there was a brief fall to ∼4 °C at around 7 Ka ago, which might be caused by a short lived expansion of local alpine glaciers. The long-term T-dependence of δD was 1.47‰/°C, identical to the value in modern precipitation.  相似文献   

Atomistic simulation of the mechanisms of noble gas incorporation in minerals     

Z. Du  N.L. Allan  J.A. Purton 《Geochimica et cosmochimica acta》2008,72(2):554-573

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.  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   

Biotite weathering and nutrient uptake by ectomycorrhizal fungus, Suillus tomentosus, in liquid-culture experiments     

Zsuzsanna Balogh-Brunstad  C. Kent Keller  Forrest Stevens  Bernard T. Bormann 《Geochimica et cosmochimica acta》2008,72(11):2601-2618

Ectomycorrhiza-forming fungi (EMF) alter the nutrient-acquisition capabilities of vascular plants, and may play an important role in mineral weathering and the partitioning of products of weathering in soils under nutrient-limited conditions. In this study, we isolated the weathering function of Suillus tomentosus in liquid-cultures with biotite micas incubated at room temperature. We hypothesized that the fungus would accelerate weathering by hyphal attachment to biotite surfaces and transmission of nutrient cations via direct exchange into the fungal biomass. We combined a mass-balance approach with scanning electron microscopy (SEM) and atomic force microscopy (AFM) to estimate weathering rates and study dissolution features on biotite surfaces. Weathering of biotite flakes was about 2-3 orders of magnitude faster in shaken liquid-cultures with fungus compared to shaken controls without fungus, but with added inorganic acids. Adding fungus in nonshaken cultures caused a higher dissolution rate than in inorganic pH controls without fungus, but it was not significantly faster than organic pH controls without fungus. The K⁺, Mg²⁺ and Fe²⁺ from biotite were preferentially partitioned into fungal biomass in the shaken cultures, while in the nonshaken cultures, K⁺ and Mg²⁺ was lost from biomass and Fe²⁺ bioaccumulated much less. Fungal hyphae attached to biotite surfaces, but no significant surface changes were detected by SEM. When cultures were shaken, the AFM images of basal planes appeared to be rougher and had abundant dissolution channels, but such channel development was minor in nonshaken conditions. Even under shaken conditions the channels only accounted for only 1/100 of the total dissolution rate of 2.7 × 10⁻¹⁰ mol of biotite m⁻² s⁻¹. The results suggest that fungal weathering predominantly occurred not by attachment and direct transfer of nutrients via hyphae, but because of the acidification of the bulk liquid by organic acids, fungal respiration (CO₂), and complexation of cations which accelerated dissolution of biotite. Results further suggest that both carbohydrate source (abundant here) and a host with which nutrients are exchanged (missing here) may be required for EMF to exert an important weathering effect in soils. Unsaturated conditions and physical dispersal of nutrient-rich minerals in soils may also confer a benefit for hyphal growth and attachment, and promote the attachment-mediated weathering which has been observed elsewhere on soil mineral surfaces.  相似文献   

Upwelling, species, and depth effects on coral skeletal cadmium-to-calcium ratios (Cd/Ca)     

Kathryn A. Matthews  Andréa G. Grottoli  James E. Palardy 《Geochimica et cosmochimica acta》2008,72(18):4537-4550

Skeletal cadmium-to-calcium (Cd/Ca) ratios in hermatypic stony corals have been used to reconstruct changes in upwelling over time, yet there has not been a systematic evaluation of this tracer’s natural variability within and among coral species, between depths and across environmental conditions. Here, coral skeletal Cd/Ca ratios were measured in multiple colonies of Pavona clavus, Pavona gigantea and Porites lobata reared at two depths (1 and 7 m) during both upwelling and nonupwelling intervals in the Gulf of Panama (Pacific). Overall, skeletal Cd/Ca ratios were significantly higher during upwelling than during nonupwelling, in shallow than in deep corals, and in both species of Pavona than in P. lobata. P. lobata skeletal Cd/Ca ratios were uniformly low compared to those in the other species, with no significant differences between upwelling and nonupwelling values. Among colonies of the same species, skeletal Cd/Ca ratios were always higher in all shallow P. gigantea colonies during upwelling compared to nonupwelling, though the magnitude of the increase varied among colonies. For P. lobata, P. clavus and deep P. gigantea, changes in skeletal Cd/Ca ratios were not consistent among all colonies, with some colonies having lower ratios during upwelling than during nonupwelling. No statistically significant relationships were found between skeletal Cd/Ca ratios and maximum linear skeletal extension, δ¹³C or δ¹⁸O, suggesting that at seasonal resolution the Cd/Ca signal was decoupled from growth rate, coral metabolism, and ocean temperature and salinity, respectively. These results led to the following conclusions, (1) coral skeletal Cd/Ca ratios are independent of skeletal extension, coral metabolism and ambient temperature/salinity, (2) shallow P. gigantea is the most reliable species for paleoupwelling reconstruction and (3) the average Cd/Ca record of several colonies, rather than of a single coral, is needed to reliably reconstruct paleoupwelling events.  相似文献   

Phthalic acid complexation and the dissolution of forsteritic glass studied via in situ FTIR and X-ray scattering     

Peter M. Morris 《Geochimica et cosmochimica acta》2008,72(8):1970-1985

Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t^1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10⁻⁶ cm² s⁻¹ in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10⁻¹² mol cm⁻² s⁻¹ (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm⁻³ to 2.2 g cm⁻³, consistent with preferential loss of Mg from the surface. Auxiliary batch experiments with forsteritic glass films deposited onto soda glass were also completed to add further constraints to the mechanism of reaction. By combining reflectivity with diffuse scatter measurements it is shown that the primary interface changes little in terms of atomic-scale roughness even after removal of several hundred angstroms of material. These measurements unequivocally show how a dicarboxylic acid bonds to and may chelate the dissolution of a magnesium-bearing silicate. At the molecular level the solid surface retreat may best be described by a depinning model where Mg is preferentially removed and residual silica tetrahedra polymerize and act to episodically “pin” the surface.  相似文献   

The composition and crystallinity of the near-surface regions of weathered alkali feldspars     

Martin R. Lee  Mark E. Hodson  Maureen MacKenzie  Caroline L. Smith 《Geochimica et cosmochimica acta》2008,72(20):4962-4975

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.  相似文献   

Geochemistry, petrology and ages of the lunar meteorites Kalahari 008 and 009: New constraints on early lunar evolution     

A.K. Sokol  V.A. Fernandes  T. Schulz  A. Bischoff  R.N. Clayton  K. Nishiizumi  L. Schultz  K. Mezger 《Geochimica et cosmochimica acta》2008,72(19):4845-4873

Kalahari 008 and 009 are two lunar meteorites that were found close to each other in Botswana. Kalahari 008 is a typical lunar anorthositic breccia; Kalahari 009 a monomict breccia with basaltic composition and mineralogy. Based on minor and trace elements Kalahari 009 is classified as VLT (very-low-Ti) mare basalt with extremely low contents of incompatible elements, including the REE. The Lu-Hf data define an age of 4286 ± 95 Ma indicating that Kalahari 009 is one of the oldest known basalt samples from the Moon. It provides evidence for lunar basalt volcanism prior to 4.1 Ga (pre-Nectarian) and may represent the first sample from a cryptomare. The very radiogenic initial ¹⁷⁶Hf/¹⁷⁷Hf (εHf = +12.9 ± 4.6), the low REE, Th and Ti concentrations indicate that Kalahari 009 formed from re-melting of mantle material that had undergone strong incompatible trace element depletion early in lunar history. This unusually depleted composition points toward a hitherto unsampled basalt source region for the lunar interior that may represent a new depleted endmember source for low-Ti mare basalt volcanism. Apparently, the Moon became chemically very heterogeneous at an early stage in its history and different cumulate sources are responsible for the diverse mare basalt types.Evidence that Kalahari 008 and 009 may be paired includes the similar fayalite content of their olivine, the identical initial Hf isotope composition, the exceptionally low exposure ages of both rocks and the fact that they were found close to each other. Since cryptomaria are covered by highland ejecta, it is possible that these rocks are from the boundary area, where basalt deposits are covered by highland ejecta. The concentrations of cosmogenic radionuclides and trapped noble gases are unusually low in both rocks, although Kalahari 008 contains slightly higher concentrations. A likely reason for this difference is that Kalahari 008 is a polymict breccia containing a briefly exposed regolith, while Kalahari 009 is a monomict brecciated rock that may never have been at the surface of the Moon.Altogether, the compositions of Kalahari 008 and 009 permit new insight into early lunar evolution, as both meteorites sample lunar reservoirs hitherto unsampled by spacecraft missions. The very low Th and REE content of Kalahari 009 as well as the depletion in Sm and the lack of a KREEP-like signature in Kalahari 008 point to a possible source far from the influence of the Procellarum-KREEP Terrane, possibly the lunar farside.  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   

Trace Element Partitioning and Accessory Phase Saturation during H2O-Saturated Melting of Basalt with Implications for Subduction Zone Chemical Fluxes   总被引：2，自引：0，他引：2  

Klimm  Kevin; Blundy  Jon D.; Green  Trevor H. 《Journal of Petrology》2008,49(3):523-553

Experimental phase equilibrium and trace element partitioningdata are reported for H₂O-saturated mid-ocean ridge basalt at2·5 GPa, 750–900°C and oxygen fugacities atthe nickel–nickel oxide buffer. Garnet, omphacite andrutile are present at all temperatures. Amphibole and epidotedisappear as residual phases above 800°C; allanite appearsabove 750°C. The Na–Al-rich silicate glass presentin all run products is likely to have quenched from a supercriticalliquid. Trace element analyses of glasses demonstrate the importantcontrol exerted by residual minerals on liquid chemistry. Inaddition to garnet, which controls heavy rare earth elements(HREE) and Sc, and rutile, which controls Ti, Nb and Ta, allanitebuffers the light REE (LREE; La–Sm) contents of liquidsto relatively low levels and preferentially holds back Th relativeto U. In agreement with previous experimental and metamorphicstudies we propose that residual allanite plays a key role inselectively retaining trace elements in the slab during subduction.Experimental data and analyses of allanite-bearing volcanicrocks are used to derive a model for allanite solubility inliquids as a function of pressure, temperature, anhydrous liquidcomposition and LREE content. The large temperature dependenceof allanite solubility is very similar to that previously determinedfor monazite. Our model, fitted to 48 datapoints, retrievesLREE solubility (in ppm) to within a factor of 1· 40over a pressure range of 0–4 GPa, temperature range of700–1200°C and for liquids with anhydrous SiO₂ contentsof 50–84 wt %. This uncertainty in LREE content is equivalentto a temperature uncertainty of only ± 27°C at 1000K, indicating the potential of allanite as a geothermometer.Silicic liquids from either basaltic or sedimentary protolithswill be saturated in allanite except for Ca-poor protolithsor at very high temperatures. For conventional subduction geothermsthe low solubility of LREE (+ Th) in liquids raises questionsabout the mechanism of LREE + Th transport from slab to wedge.It is suggested either that, locally, temperatures experiencedby the slab are high enough to eliminate allanite in the residueor that substantial volumes of H₂O-rich fluids must pass throughthe mantle wedge prior to melting. The solubility of accessoryphases in fluids derived from subducted rocks can provide importantconstraints on subduction zone thermal structure. KEY WORDS: subduction; experimental petrology; allanite; solubility; supercritical liquid; eclogite  相似文献