Search Results - (Author, Cooperation:C. M. Henderson)

2011-11-19

American Association for the Advancement of Science (AAAS)

0036-8075

1095-9203

Biology

Chemistry and Pharmacology

Computer Science

Medicine

Natural Sciences in General

Physics

Animals ; *Biodiversity ; Carbon Dioxide ; Carbon Isotopes ; China ; *Ecosystem ; *Extinction, Biological ; Fires ; *Fossils ; Geologic Sediments ; Invertebrates/classification ; Isotopes ; Lead ; Mass Spectrometry ; Methane ; Oceans and Seas ; Plants/classification ; Radioisotope Dilution Technique ; Radiometric Dating ; Seawater/chemistry ; Time ; Uranium ; Vertebrates/classification

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract Mineral compositional relationships have been studied in a variety of alkaline basic rocks from small, highlevel intrusions. These small intrusions must have cooled quickly as the phases are all zoned, especially those forming the matrix of some of the rocks which seem to have formed under conditions of almost perfect fractional crystallization. The compositions of nephelines from the various rocks define an overall evolutionary trend in which Na2O, K2O and CaO decrease and SiO2 increases. The most SiO2-rich nephelines plot in the nepheline plus feldspar stability field and must have crystallized metastably from the melt. Clear, interstitial analcime is definitely not a primary phase. It appears to be restricted to rocks which crystallized primary SiO2-rich nepheline and formed from this phase by subsolidus recrystallization processes. Most of the rocks studied appear to have crystallized plagioclase as the first felsic mineral. In some rocks this phase is zoned from ∼An70-60, through anorthoclase compositions to rims of composition ∼Or50 and this is the only feldspar present in the rocks. In other rocks the “plagioclase” shows zoning to similarly potassic compositions (Or40–50) but this is accompanied by separate grains of orthoclase cryptoperthite. The zoning trends of the coexisting “plagioclase” and alkali feldspar allow the feldspar critical end point compositions to be estimated for these rocks. Rocks containing strongly zoned plagioclase as the only feldspar species are believed to have evolved towards relatively K2O-rich low-temperature melting compositions due to the presence of mafic components. The crystallization histories of the rocks are considered in terms of three planes in the An-Ne-Ks-Qz system i.e. Ne-Ks-Qz; (Ne60Ks40)-An-Qz; and An-Ab-Or. Mineral and bulk rock compositional data together with textural criteria are used to modify phase equilibrium relations in these simple experimental systems to take account of the additional components (e.g. mafics) present in natural magmas.

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1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract The Ascutney Mountain complex of eastern Vermont, USA, is a composite epizonal pluton of genetically related gabbro to granite intrusives. Nd isotopic data are reported for mafic rocks, granites, and nearby country rock. The parental mafic magma producing the complex 122 m.y. ago had 87Sr/86Sr=0.7039, 143Nd/144Nd=0.512678 (ɛ Nd=+3.8) and δ 18O=6.1‰, indicating a mantle source with time-integrated lithophile element depletion. Uniform initial radiogenic isotope ratios for granites, which are undistinguishable from those for the most primitive gabbro, suggest that the granite magma evolved from the mafic magma without crustal contamination and that the increase in δ 18O, to about 7.8‰, is the result of fractional crystallization. Mafic rocks show a large range in initial 143Nd/144Nd ratio, from about 0.51267 to 0.51236 (ɛ Nd= +3.7 to −2.5), which is correlated with elevated 87Sr/86Sr ratios and δ 18O. These data substantiate the production of mafic lithologies by fractional crystallization of the parental magma accompanied by assimilation of up to about 50% crust. The local country rocks include gneiss and schist and assimilation involved representatives of both rock types. The isotopic and chemical relationships preclude derivation from a single batch of magma undergoing contamination and indicate that a large magma body at depth evolved largely by fractionation with batches of melt issued from this chamber being variably contaminated at higher levels or at the level of emplacement. The Precambrian gneisses of the Chester dome and overlying lower Paleozoic schists have essentially identical Nd isotope systematics which suggest a crustal formation age of about 1.6. b.y. The parental sediments for the schists were apparently derived from a protolith similar to the gneissic basement without appreciable Sm/Nd fractionation.

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1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract The Ascutney Mountain igneous complex in eastern Vermont, USA, is composed of three principal units with compositions ranging from gabbro to granite. Sr and O isotopic and major element relationships for mafic rocks, granites, and nearby gneissic and schistose country rock have been investigated in order to describe the petrogenesis of the mafic suite which ranges from gabbro to diorite. The entire complex appears to have been formed within a short interval 122.2±1.2 m.y. ago. The granites with δ 18O near +7.8‰ had an initial 87Sr/86Sr of 0.70395(±6) which is indistinguishable from the initial ratio of the most primitive gabbro. Initial 87Sr/86Sr ratios and δ 18O values for the mafic rocks range from 0.7039 to 0.7057 and +6.1 to +8.6‰, respectively. The isotopic ratios are highly correlated with major element trends and reflect considerable crustal contamination of a mantle-derived basaltic parent magma. The likely contaminant was Precambrian gneiss similar to exposed bedrock into which the basic rocks were emplaced. A new approach to modelling of assimilation during the formation of a cogenetic igneous rock suite is illustrated. Chemical and isotopic modelling indicate that the mafic rocks were produced by simultaneous assimilation and fractional crystallization. The relative amounts of fractionation and assimilation varied considerably. The mafic suite was not produced by a single batch of magma undergoing progressive contamination; rather, the various rocks probably were derived from separate batches of magma each of which followed a separate course of evolution. The late stage granite was apparently derived from basaltic magma by fractionation with little or no crustal assimilation. The early intrusive phases are much more highly contaminated than the final one. The observed relationships have important implications for the formation of comagmatic complexes and for isotopic modelling of crustal contamination.

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0022-4545

Psychology

Sociology

1476-4687

Nature Archives 1869 - 2009

Biology

Chemistry and Pharmacology

Medicine

Natural Sciences in General

Physics

[Auszug] It has been recognized for some time that non-equilibrium cation ordering in minerals might provide a means to measure rock cooling rates, from early work on Mg/Fe ordering in amphi-boles6 and extensive studies of pyroxenes7'8 to more recent analysis of Al/Si ordering in alkali feldspars9. ...

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1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract Metal K- and L3-, sulfur K- and arsenic K- and L3-edge X-ray absorption near-edge spectra of a series of metal disulfides, FeS2 (both pyrite and marcasite), CoS2, NiS2, and CuS2, and their isomorphs, FeAsS and CoAsS, are presented. The features in this region of these spectra are interpreted using band structure and molecular orbital calculations in terms of the transitions from the 1s or 2p3/2 state to unoccupied states. The 3d transition metal L3-edge spectra of these materials show dependence on the degree of multiplet splitting in the final state, and thus offer less information on the electronic ground state. There are substantial differences in the spectra of the isostructural materials, whereas the spectra of the isotopes pyrite and marcasite show several similarities, illustrating the dependence of near-edge region on electronic structure.

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1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract Thermal expansion data, determined by powder X-ray diffraction methods are presented for 11 members of the (Li,Na,K,Rb)8(Al6Si6O24)Cl2 solid solution series, 3 members of the (Na,K)8(Al6Si6O24)Br2 solid solution series and Na8(Al6Si6O24)I2. Only the latter showed a discontinuity in its expansion curve at 810° C wigh a mean linear expansion coefficient of 22.0×10−6 °C−1 below and 7.7×10−6 °C−1 above the discontinuity. The mean expansion coefficients from 0° to 500° C decrease gradually over the range of room temperature cell edges from 8.4 to 8.89 Å, then increase up to a cell edge of 9.01 Å above which they decrease sharply and extrapolate to a zero coefficient at 9.4 Å. These variations may be related to the expansion characteristics of the bonds between the cavity cations and cavity anions in different sodalites. The aluminosilicate-sodalites which show a discontinuity in their thermal expansion curves are those with large cavity anions, I− or SO 4 2− ; the discontinuity is believed to occur at the point when the x-coordinate of the cavity cation becomes 0.25.

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1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract A type of hysteresis, similar to that observed in the heat capacity measurements (Openshaw et al., 1979), has been found in the room temperature unit cell parameters of a microcline sample 71104 and likewise indicates the existence of two forms of this microcline. The A-form (obtained on cooling the sample to approximately 80 K) has significantly different values of b, β and V to the B-form which is the more stable form above 300±10 K. The transition from the A- to the B-form occurs over a period of months and has an associated ΔV of −0.0011 nm3. The cell parameters of the B-form have been measured up to 1278 K and show significant changes: a and V increase, b constracts, and c is unchanged on increasing temperature. The calculated thermal expansion ellipsoid is nearly uniaxial and similar in shape to that for sanidine. Below room temperature the isobaric thermal expansion coefficent αp, for a natural microcline is nearly four times as large as that for sanidine. Above room temperature αp for 71104 microcline decreases markedly with increasing temperature. This implies a rapid change in the thermal expansion behavior of microcline which has been correlated with the proposed phase transition.

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract A computer model for cubic sodalite structures, general formula M 8(T 12O24)X 2 where M, X and T are the cavity cation and anion and framework cation respectively, has been devised. It has been used to determine the effect of changing cavity cation and anion radii on the cell edge, tilt angle of the tetrahedra and T-O-T angle for the following sodalite frameworks: (Al6Si6O24)6−, (Be6Si6O24)12−, (Al12O24)12−, and (B12O24)12−. After fixing the T-O distance(s), the cavity cation-framework oxygen distance and taking a value of 1.4 Å for the radius of oxygen the model was used to calculate atomic coordinates and interatomic distances and angles for selected aluminosilicate-sodalites. The structure calculated for Na8(Al6Si6O24)Cl2 agrees closely with that determined for natural sodalite (Löns and Schulz, 1967). The model is also applied to the estimation of the effective radii of the tetrahedrally-coordinated cavity anions which can be accommodated in natural and synthetic sodalites: OH− 1.48–1.51, Cl− 1.78, Br− 1.93, I− 2.14–2.17, SO 4 2− 2.37–2.57, MoO 4 2− 2.70 and WO 4 2− 2.79 Å.

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract 2p (L 2,3) X-ray absorption spectra are presented for a range of minerals to demonstrate the usefulness of L-edge spectroscopy as a symmetry- and valenceselective probe. 2p XAS provides a sensitive fingerprint of the electronic states of 3 d transition metals and can be applied to phases containing mixtures of such elements. Calculated spectra for 3d n → 2p 5 3d n+1 transitions provide a basis for the interpretation of the measured spectra. Thus, in principle, multiple valence states of a particular 3 d metal can be precisely characterized from a single L-edge spectrum. Examples of vanadium L-edge spectra are presented for a range of minerals; these complex spectra hold information concerning the presence of vanadium in multiple valence states. The Cu L-edge spectrum of sulvanite (Cu3 VS4) indicates the presence of both Cu+ and Cu2+; the V L-edge spectrum of the same sample shows that both V2+ and V5+ are present. Spectral simulations representing mixtures of Fe d 5 and Fe d 6 states are used to quantify Fe3+/∑Fe in a spinel, a glass, and an amphibole, all of which contain Fe as a major component. To illustrate the sensitivity of 2p XAS in a dilute system, the Fe L-edge spectrum of amethyst (α-SiO2: Fe) has been recorded; this spectrum shows that ∼68% of the Fe in amethyst is Fe2+, and ∼32% is Fe3+. Although previous studies on amethyst using other spectroscopic methods cite evidence for Fe4+, there is no indication in the L-edge spectrum for Fe4+ in amethyst. Comparison of theoretical and experimental spectra not only allows the valence states of 3 d ions to be recognised, but also provides site-symmetry information and crystal field parameters for each ion site.

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract A number of leucite group materials with the formula X2YSi5O12 where X=K, Rb, Cs and Y=Mg, Zn, Cd have been synthesized by dry and hydrothermal crystallization of glass starting materials. 29Si MASNMR has been used to obtain structural information, such as the number of distinct tetrahedral sites, degree of cation ordering, and estimates of the mean T-O-T bond angles of the tetrahedra. X-ray powder diffraction gave information on cell volumes and degree of distortion from cubic symmetry for all the samples and space group and structural information for some samples. Integration of the different length-scale data obtained using these two complementary techniques allows greater reliance to be placed on the structures deduced for these leucite samples, which are only available as fine-grained powders. Hydrothermally synthesized K2MgSi5O12, K2ZnSi5O12 and Rb2ZnSi5O12 have structures with 12 distinct tetrahedral sites (T-sites) and are monoclinic P21/c while the dry-synthesized equivalents are disordered with single T-sites and are cubic, Ia3d. Most of the other members of the group have structures with 6 tetrahedral sites with Cs2CdSi5O12 being orthorhombic, Pbca. Cs2ZnSi5O12 has an intermediate “5+2” structure. Decreasing the size of the X+ cation for a given Y2+ cation gives more collapsed and distorted frameworks. 133Cs NMR was used to show that samples with 6 T-sites have 2 alkali sites. It is deduced that samples with 12 T-sites will undergo a displacive phase transition to a 6 T-site structure (possibly via a 5+2 intermediate in some cases) with no change in the framework topology or degree of T-site ordering.

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract Phases with the composition K2MgSi5O12, belonging to the leucite structure group were synthesised under dry and hydrothermal conditions and studied using 29Si NMR. The 29Si spectrum for the dry-crystallised material (which is cubic) consists of a single broad line, suggesting a high degree of disorder. The hydrothermally crystallised material (which is probably monoclinic, with a distorted leucite lattice) has a 29Si spectrum which consists of ten lines of equal intensity, two of which have small chemical shift anisotropies and are therefore assigned to Q4(4Si) sites. These data have been interpreted in terms of a structure with 12 distinct tetrahedral sites over which 2 Mg atoms and 10 Si atoms are fully ordered. A 2-dimensional COSY spectrum shows correlations between some Q4(3Si) silicon atoms and two other Q4(3Si) silicon atoms. This fully constrains the topology of the unit cell. Two schemes of Si/Mg ordering over the unit cell can give good fits to the COSY spectrum. Using the tetrahedral (T) site notation defined for natural tetragonal leucite, the first of these arrangements involves Mg and Q4(4Si) silicon atoms each occupying one T1-type site and one T3-type site, and Q4(3Si) silicons occupying the remaining sites, i.e. four T2-type sites, two T1-type sites and two T3-type sites. In the second arrangement, the T2-type sites are occupied by Mg atoms and Q4(4Si) silicon atoms and all the T1-and T3-type sites are occupied by Q4(3Si) atoms.

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract The X-ray absorption spectra of the transition metal L3,2-edges of the dichalcogenides FeS2 (pyrite), FeSe2, FeTe2, CoS2, CoSe2, CoTe2, NiS2, NiSe2 and NiTe2 have been studied. These spectra are compared with theoretical simulations make using the atomic multiplet approach assuming on octahedral site for the metal atoms. The Ni spectra can be closely simulated using this approach but the Fe and Co spectra show less good fits to the experimental data. The reasons for this and its implications for the use of L-edge spectra in the study of such minerals are discussed in terms of the covalency and the ground states of the compounds; these results indicate the mixing of the ground states increases in the order Ni〈Co〈Fe.

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract The solid solution sanmartinite (ZnWO4)—cuproscheelite (CuWO4) has been studied using Cu 2p X-ray absorption spectroscopy. While a single L3 absorption peak is observed for CuWO4, two distinct L3 absorption peaks with a separation of ∼0.8 eV are observed for the intermediate samples in the solid solution. The two peaks represent distinct Cu sites: one with all CuO6 next nearest neighbours in the (Cu,Zn)O6 chains, another having at least one ZnO6 next nearest neighbour. Both sites show a linear increase in covalency as a function of increasing Cu-content. The relative intensities of the two absorption peaks is dependent upon the Cu-content and has been used to model the site occupancies. The results reveal that the local structural effects can be associated with a composition-dependent structural phase transition from P2/c (ZnWO4) to P $$\bar 1$$ (CuWO4). Deviations from a single-site model are explained in terms of the local environments, and evidence for site preferences and local clustering are explored.

Electronic Resource

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract Carbonate phases, some rich in Na2O and comparatively rich in SrO and BaO, occur as inclusions in perovskite and calzirtite (Ca2Zr5Ti2O16) in the carbonatite of the Guli complex, Siberia. This is the first record of alkali carbonates, akin to ‘nyerereite’ [Na2Ca(CO3)2], in plutonic igneous rocks. The inclusion populations suggest that the parental magma of the complex was Ca-rich but developed Na-rich differentiates during the latest stages. This points to the dominant calcic carbonatites of the complex not being derivatives of alkali-rich parental carbonatites. These alkali-rich carbonate inclusions (and rare inclusions of djerfisherite) have been preserved due to the resistance of perovskite and calzirtite to processes of leaching, hydrothermal alteration and weathering.

Electronic Resource

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract The Shiant Isles Main Sill of the British Tertiary Igneous Province is a classic example of a differentiated, alkaline basic sill. Four separate intrusions, each emplaced internally in rapid succession, form a 165-m-thick sill hosted by Lower Jurassic sedimentary rocks. Extensive Nd and Sr isotopic studies were conducted on samples from a vertical section through the sill where the relationships of samples to one another are well defined. The results illuminate patterns of modification of isotopic ratios and clarify the petrogenesis (magma sources, crustal contamination), magmatic processes (bulk mixing, interstitial liquid mixing), and post-magmatic alteration (hydrothermal effects on Sr and Nd). Overall, the whole-rock initial 87Sr/86Sr ratios range from ∼0.7037 to 0.7061 while initial 143Nd/144Nd ratios vary from ∼0.51243 to 0.51286 (ɛNd∼−0.7 to +5.7) – values that contrast markedly with those of the country rock. Acid leaching (HCl) of the whole-rock samples that removes analcime indicates that most of the scatter in the 87Sr/86Sr is caused by the ubiquitous sub-solidus, aqueous alteration during which more-radiogenic Sr was introduced into the sill, especially along the margins, and also reveals magmatic isotopic ratios. In contrast, Nd was immobile during fluid interaction so that the sill 143Nd/144Nd ratios were not affected, even 〈1 m from the country-rock contact. Using leached rock values, 87Sr/86Sr and 143Nd/144Nd ratios are inversely correlated from magmatic processes. Magmas with two distinct isotopic compositions were involved: a more primitive one with 143Nd/144Nd ∼0.51285 and 87Sr/86Sr ∼0.7035 that produced the first two intrusions and a more evolved one (with 0.51252 and 0.7048) that produced the third intrusion. Mixing of the two magmas was very limited, restricted to near contacts between units, and apparently occurred by interstitial melt migration. The more evolved crinanitic magma was probably produced from a batch of the more primitive picritic melt by a small degree of crustal contamination and crystal fractionation during a short crustal residence prior to ascent and emplacement.

Electronic Resource

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract The Mount Brome complex of the Monteregian province of southern Quebec, Canada, consits of several major intrusions ranging compositionally from gabbro to syenite. The relative ages of these intrusives have been investigated with high-resolution 40Ar/39Ar analyses, including a specially designed irradiation configuration to cancel the effects of fluence gradients. Small yet distinct apparent age differences are observed. While a number of analytical and geological factors could be proposed to explain the small variations, evaluation of these suggests the age differences reflect those in emplacement times. The gabbro and nepheline diorite were emplaced within a short span 123.1 Ma ago. Generally more evolved lithologies (biotite monzodiorite, pulaskite, nordmarkite) appear to have been emplaced within a restricted interval 1.4±0.3 Ma later. Whole-rock Rb-Sr systematics do not give acceptable isochrons because of significant scatter interpreted to reflect initial 87Sr/86Sr heterogeneities resulting from crustal contamination. Considering the variations in initial ratio, the Rb-Sr data are consistent with the 40Ar/39Ar age.

Electronic Resource

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract Electron and ion-probe microanalysis have been used to obtain zoning profiles for major and trace elements in olivine phenocrysts from a high-magnesian andesite from Shodo-Shima island, southwest Japan. This rock was previously thought to represent undifferentiated, primary magma. Some crystals have unzoned cores, while others show cores which are reversely zoned with respect to Mg/ (Mg+Fe), Ni, Mn and Cr. In addition, some Ni profiles show a normally zoned “hump” at the most central portions of the reversely zoned crystals. All crystals show normally zoned rims. The Li concentrations are constant throughout the cores of all crystals studied, but rise sharply, by a factor of up to at least six, in the rims. The Ca and Co concentrations are essentially constant throughout all the crystals. Mechanisms for producing the observed zoning profiles are discussed, and it is concluded that the reverse zoning was produced by the introduction of crystals into a less differentiated magma than that in which they grew. The reversely zoned crystals could therefore represent xenocrysts which were introduced into an undifferentiated magma, or phenocrysts introduced into a more primitive magma by a magma mixing process. The Ni profiles are used to estimate the residence time of these crystals in the more primitive magma. The following trace element partition co-efficients have been estimated for the olivine-groundmass system in this rock: D Ni=16; D Mn=1.1; D Co=4.2; D Ca =0.02; D Ti=0.005; D V=0.05; D Sc=0.2; D Na=0.0002. Studies of trace element zoning will become increasingly important as the new generation of trace element microprobes become available but a larger database of experimentally determined values for trace element partition coefficients and diffusion coefficients in crystals and magmas, and a better understanding of other disequilibrium processes are required to fully exploit the new data.

Electronic Resource

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract The structural environments of Mn2+ and Sr2+ at concentrations of 0.2–0.8 wt% in dry and hydrous silicate glasses have been studied using X-ray absorption spectroscopy (EXAFS and XANES). The environment of Mn in hydrous silica glasses containing 4.5 and 6.0 wt% H2O appears to be close to an undistorted octahedral site, whereas Mn in other compositions, both dry and hydrous, occupies either a distribution of octahedral and tetrahedral sites, or distorted, non-centrosymmetric sites. The fraction of non-centrosymmetric sites (including tetrahedral) or the average degree of distortion of the sites decreases with both increasing dissolved water concentration and number of non-bridging oxygens in the glass. For Sr the changes as a function of polymerisation and water concentration are less clear, but it appears that the average Sr-O distances are shorter than in crystalline silicates and decrease further with decreasing polymerisation. The structural data obtained in this study are not readily integrated with previous partitioning data for Mn, suggesting that changes in the first-shell coordination geometry of Mn do not play a direct role in controlling the melt compositional dependence of trace element partition coefficients. It is tentatively suggested that distortions of the framework resulting from the incorporation of Mn (i.e. a second shell effect) control the partitioning behaviour.

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