Fossil-pollen evidence for abrupt climate changes during the past 18 000 years in eastern North America

A quantitative measure of the rate at which fossil-pollen abundances changed over the last 18 000 years at 18 sites spread across eastern North America distinguishes local from regionally synchronous changes. Abrupt regional changes occurred at most sites in late-glacial time (at 13700, 12 300, and 10000 radiocarbon yr BP) and during the last 1000 years. The record of abrupt late-glacial vegetation changes in eastern North America correlates well with abrupt global changes in ice-sheet volume, mountain snow-lines, North Atlantic deep-water production, atmospheric CO₂, and atmospheric dust, although the palynological signal varies from site to site. Changes in vegetation during most of the Holocene, although locally significant, were not regionally synchronous. The analysis reveals non-alpine evidence for Neoglacial/Little Ice Age climate change during the last 1000 years, which was the only time during the Holocene when climate change was of sufficient magnitude to cause a synchronous vegetational response throughout the subcontinent. During the two millennia preceding this widespread synchronous change, the rate of change at all sites was low and the average rate of change was the lowest of the Holocene.Contribution to Clima Locarno Past and Present Climate Dynamics; Conference September 1990, Swiss Academy of Sciences — National Climate Program     

Time resolved simulation of lightning by lip

In this letter, we report results of time resolved spectra of lightning simulation in air by laser-induced plasma (LIP). The measured electron temperatures varied from (1.7 +/- 0.1)X10(4) K at 600 ns to (1.2 +/- 0.1)X10(4)K at 4 microseconds after the ignition of the plasma. Electron densities in the plasma varied from (7.0 +/- 1.4)X10(17)/cm3 to (9.0 +/- 1.8)X10(16)/cm3 for the above times. We also present, for the first time, a comparison of state variables for LIP and natural lightning. We find that immediately following the ignition both natural lightning and LIP reach temperatures in excess of 16,000K and relax to ambient pressure with different rates. They are expected to approach 2000 - 4000 K temperature range, which is important to chemical synthesis, in an asymptotically similar fashion.     

Geochemical stratigraphy of the Huronian continental volcanics at Thessalon,Ontario: contributions of two-stage crustal fusion

The 1500 m thick sequence of Huronian continental volcanics at Thessalon, Ontario is subdivided into 4 volcanic cycles, each of which includes abundant early mafic end-members, central intermediate flows, and late rhyolite units. Major and trace element concentrations are dominated by extensive gabbroic fractionation trends that ultimately produced two types of felsic flows: (1) rhyolites with high light rare earth element (LREE) and relatively low large-ion lithophile element (LILE) concentrations (high-LREE, low-LILE rhyolites), and (2) following late separation of REE-rich accessory phases, rhyolites depleted in LREE (low-LREE, high-LILE rhyolites). Mafic end-members of individual volcanic cycle are progressively less siliceous and less enriched in LILE and LREE with height in the stratigraphic section. Ti/Zr ratios gradually rise from 35 in early mafic flows to stabilize at about 85 in late units, while average SiO₂ contents decrease from 56 to about 50% and Mg# rises from about 48 to 52. -Nd values are consistently negative, indicating variable degrees of pre-fractionation crustal contamination of the end-member magmas during their uprise through the crust. Mixing models are consistent with up to 50% contamination by crustal material of tonalitic hornblende-gneiss composition. A progressive increase in -Nd, from about-5.0 to-0.5 upward in the volcanic succession, reflects a decreasing degree of crustal contamination due to development of insulating layers along margins of the feeder system. Detailed stratigraphic variations suggest that successive magmas batches were intercepted by a progressively fractionating, periodically replenished magma source, giving rise to open-system magmatism. Despite the prevalence of crustal assimilation in the Huronian lavas, (La/Sr)N ratios are too low in least contaminated end-members to be explained by contamination of tholeiitic magmas. The late basalts resemble instead modern island are basalts, and it is suggested that the subcontinental mantle source was enriched by subduction-related processes during crustal formation. Within individual volcanic cycles gabbroic fractionation trends systematically deviate from calculated factors toward compositions characteristic of hornblende-gneiss. Such relations suggest that further crustal contamination of the magmas occurred simultaneous with crystal fractionation. probably within undulating sills at upper crustal levels. Quantitative analysis suggests assimilation/fractional crystallization (A/FC) ratios of about 0.45. As a result of extensive two-stage contamination, rhyolites from the initial volcanic cycle incorporate a total of over 60% of crust.     

Fractional Crystallization and Liquid Immiscibility Processes in the Alkaline-Carbonatite Complex of Juqui (So Paulo, Brazil)

The Juqui circular intrusion, which is Cretaceous in age (130–135Ma), crops out in the Precambrian gneissic basement in Brazilover an area of 14 km2. It consists of olivine clinopyroxen-itecumulates (with minor olivine gabbros) in the northeastern sector(74 vol.%), whereas ijolites-melteigites-urtites (4%) and nephelinesyenites with minor essexites and syenodiorites (21%) outlinesubannular concentric patterns with an Mg-carbonatite core (1%), in the southwestern part of the complex. Petrographical, bulk rock, and mineral compositional trendsindicate that the origin of the complex can be largely accountedfor by shallow-level fractional crystallization of a carbonatedbasanitic parental magma. Such a magma was generated deep inthe subcontinental lithosphere by low-degree partial meltingof a garnet-phlogopite peridotite source. Mass-balance calculations in agreement with field volume estimatespermit definition of several fractionation stages of the magmaticevolution under nearly closed-system conditions, with inwarddevelopment of zonally arranged side-wall cumulates. These stagesinvolved: (1) fractionation from basanite to essexite magma(liquid fraction F = 33–5%) by crystallization of olivineclinopyroxenite plus minor olivine alkali gabbro cumulates;(2) derivation of the least differentiated mafic nepheline syenite(F = 5–5 %) from essexitic magma by subtraction of a syenodioriteassemblage; (3) exsolution of a carbonatite liquid (5%) froma CO₂-enriched mafic nepheline syenite magma, which also underwentcontinuous fractionation giving rise to ijolite-melteigite-urtitecumulates. The proportion of cumulus clinopyroxene and biotiteand intercumulus nepheline and alkali feldspar in these lastrocks, as well as the absence of alkalis in carbonatite, maybe attributed, at least in part, to loss of alkali-rich hydrousfluids released during and after the unmixing formation of thetwo conjugate liquids. The KD values determined for Mg-carbonatite/nepheline syeniteare lower (1–4–2–9) for light rare earth elements(LREE) than for REE from Eu to Yb (4–6–7–8),in contrast to recent experimental results (Hamilton et al.,1989). A possible explanation is that Juquia Mg-carbonatiterepresents an alreadydifferentiated magma, which underwent extensivefractionation of LREE-enriched calcite. In this way, the highvariability of K₀ REE patterns observed in several alkaline-carbonatitecomplexes can also be accounted for. The remarkably constant initial ⁸⁷Sr/⁸⁶Sr ratios (mostly between0–7052 and 0–7057) support the interpretation ofthe intrusion as having been generated by fractrional crystallizationand liquid immiscibility from a common parental magma. Iligherisotopic ratios (0–7060–0–7078), found mainlyin dykes and in the border facies of the intrusion, may be dueto contamination by the gecissic basement.     

Thermal expansion and spontaneous strain associated with the normal-incommensurate phase transition in melilites

The linear thermal expansions of åkermanite (Ca₂MgSi₂O₇) and hardystonite (Ca₂ZnSi₂O₇) have been measured across the normal-incommensurate phase transition for both materials. Least-squares fitting of the high temperature (normal phase) data yields expressions linear in T for the coefficients of instantaneous linear thermal expansion, $$\alpha _1 = \frac{1}{l}\frac{{dl}}{{dT}}$$ for åkermanite: $$\begin{gathered} \alpha _{[100]} = 6.901(2) \times 10^{ - 6} + 1.834(2) \times 10^{ - 8} T \hfill \\ \alpha _{[100]} = - 2.856(1) \times 10^{ - 6} + 11.280(1) \times 10^{ - 8} T \hfill \\ \end{gathered} $$ for hardystonite: $$\begin{gathered} \alpha _{[100]} = 15.562(5) \times 10^{ - 6} - 1.478(3) \times 10^{ - 8} T \hfill \\ \alpha _{[100]} = - 11.115(5) \times 10^{ - 6} + 11.326(3) \times 10^{ - 8} T \hfill \\ \end{gathered} $$ Although there is considerable strain for temperatures within 10° C of the phase transition, suggestive of a high-order phase transition, there appears to be a finite ΔV of transition, and the phase transition is classed as “weakly first order”.     

Computation of surface energies in an electrostatic point charge model: I. Theory

The attachment energies, the slice energies and the specific surface energies can be calculated in an electrostatic point charge model using the formula derived by Madelung for the potential introduced by an infinite row of equally spaced point charges. Power series are given for the Hankel function iH ₍₀₎ ⁽¹⁾ (iy) and Ψ(x)=d ln x!/dx. The logarithmic expression in the Madelung formula converges rapidly when applying a power series, which combines equally charged cations and anions. Besides the specific surface energy (γ ^hkl), the slice energy (E _s ^hkl ) and the attachment energy (E _a ^hkl ) can be considered as special categories of surface energies as they depend on surface configurations as well. The specific surface energy γ is the energy per unit area of surface needed to split the crystal parallel to a face (hkl). The attachment energy (E _a) is the energy released per mole, when a new slice of thickness d _hkl crystallizes on an already existing crystal face (hkl). The growth rate of the crystal face (hkl) is a function of its attachment energy. The slice energy (E _s) is the energy released per mole, when a new slice d _hkl is formed from the vapour neglecting the influence of edge energies. The lattice energy (E _c) which is the energy released per mole of a crystal crystallizing from the vapour, is given by the following relation: E _c=E _a+E _s.     

Structure of the αFexAl1:xOOH solid solution

The three-dimensional local organisation around Fe atoms in a natural diaspore (Al_0.9955Fe_0.0045OOH) has been investigated by angular measurements of X-ray absorption spectra. It is demonstrated that in a single crystal of diaspore, the absorption cross-section exhibits the special case of trichroism where three independent measurements are needed to determine the absorption cross-section for any direction of polarization. Extended X-ray absorption fine structure (EXAFS) spectra were thus recorded at the following orientations of the polarization vector: , , and . The incoming white beam was monochromatized using two Si(331) crystals, which deliver at the Fe K-edge a completely linearly polarized X-ray beam. The reliability of our measurements was checked by comparing the isotropic EXAFS spectrum calculated from the three orthogonal measurements to the one of the diaspore powder recorded at the magic angle. It is shown that Fe³⁺ ions are not randomly distributed within the diaspore framework. Furthermore, only part of the Fe³⁺ ions substitutes Al, the others being located in the channels of the structure. The 3D local structure of the Fe domains has been modeled assuming hematite-like clusters of three Fe octahedra topotactically grafted to aluminous chains. These Fe clusters are thought to represent ancient multinuclear Fe surface complexes having formed at the time of the diaspore growth, and being sealed in its bulk structure. The whole crystal of diaspore is then thought to have kept the memory of the heterogeneous nucleation mechanism of these hematite nuclei. In addition to the well-known examples of atom segregations, ion vacancies, and intergrowths of discrete phases, this new type of crystal defect represents another evidence of non-equilibrium crystallization process under the thermodynamic and kinetic conditions that prevail at the earth's surface.     

Computation of surface energies in an electrostatic point charge model: II. Application to zircon (ZrSiO4)

The attachment energies, the slice energies and the specific surface energies can be calculated in an electrostatic point charge model using the formula derived by Madelung for the potential introduced by an infinite row of equally spaced point charges. Power series are given for the Hankel function iH ₍₀₎ ⁽¹⁾ (iy) and (x)=d ln x!/dx. The logarithmic expression in the Madelung formula converges rapidly when applying a power series, which combines equally charged cations and anions. Besides the specific surface energy ( ^hkl), the slice energy (E _s ^hkl ) and the attachment energy (E _a ^hkl ) can be considered as special categories of surface energies as they depend on surface configurations as well. The specific surface energy is the energy per unit area of surface needed to split the crystal parallel to a face (hkl). The attachment energy (E _a) is the energy released per mole, when a new slice of thickness d _hkl crystallizes on an already existing crystal face (hkl). The growth rate of the crystal face (hkl) is a function of its attachment energy. The slice energy (E _s) is the energy released per mole, when a new slice d _hkl is formed from the vapour neglecting the influence of edge energies. The lattice energy (E _c) which is the energy released per mole of a crystal crystallizing from the vapour, is given by the following relation: E _c=E _a+E _s.     

Synthesis and stability of bastnaesites in a part of the system (Ce,La)-F-H-C-O

Summary Bastnaesites of Ce and La and their OH-analogs were synthesized and their stability relations were determined atPf = 1 kbar andT = 400 to 900°C in a part of the system (Ce,La)-F-H-C-0. The initial fluid compositions were such that and HF/(HF + H₂O) ratios were 0 to 0.172. XRD and IR studies indicate that bastnaesites equilibrated in initial fluids low in HF are all F-enriched. The hydroxylbastnaesite-(La) is stable up to 810°C and the fluorbastnaesite-(La) is stable up to 860°C. Their condensed breakdown products are La₂O₂CO₃ and LaOF, respectively. The stability of Ce bastnaesites is slightly dependent. The hydroxylbastnaesite-(Ce) is stable up to 660°C at the defined by the IQF buffer and up to 640°C by the MH buffer. The fluorbastnaesite-(Ce) is stable up to 800°C at the defined by the IQF and up to 760°C by the MH buffer. The condensed breakdown product for the hydroxyl end-member is simply CeO₂ but for the fluorine one is a combination of CeO₂, CeF₃, and CeOF. Factors, such as OH vs F, , and bulk composition, that affect the stability of individual species are discussed. Petrogenic implications resulting from the present study include that bastnaesites can be stable from hydrothermal to magmatic conditions, that F-enriched species can form in an environment relatively low in F content, and that OH-species are rare and occur only in low-temperature environments essentially devoid of F.

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Synthese und Stabilität von Bastndsil in einem Teil des Systems (Ce,La)-F-H-C-O

Zusammenfassung Ce- und La-Bastnäsite, sowie deren OH-Analoga wurden synthetisiert und ihre Stabilitätsbeziehunger beiP _f = 1 kbar undT = 400 bis 900°C wurden im System (Ce,La)F-H-C-O bestimmt. Die anfänglichen Flüssigkeitszusammensetzungen waren so, daß und die HF/(HF + H₂O)-Verhältnisse 0–0.172 waren. Röntgenpulver- und Ultrarot-Untersuchungen zeigten, daß Bastnäsite, die mit anfänglich HF-armen Flüssigkeiten equilibriert wurden, alle an F angereichert sind. Hydroxilbastndsit-(La) ist bis 810°C und Fluorbastnäsit-(La) bis 860°C stabil. Ihre festen Zersetzungsprodukte sind La₂O₂O₃, bzw. LaOF. Die Stabilität der Ce-Bastnäsite hängt etwas von ab. Hydroxilbastnäsit-(Ce) ist bei des Eisen-Quarz-Fayalit-Puffers bis 660°C stabil und mit Magnetit-Hämatit-Puffer bis 640°C. Das feste Zerfallsprodukt ist für das Hydroxil-Glied nur CeO₂, für das Fluor-Glied eine Mischung aus CeO₂, CeF₃ und CeOF. Faktoren, welche die Stabilität der einzelnen Spezies beeinflussen, werden diskutiert, wie das Verhältnis OH zu F, und die Gesamtzusammensetzung. Petrogenetische Folgerungen aus der vorliegenden Studie schließen ein, daß Bastnäsite von hydrothermalen bis zu magmatischen Bedingungen stabil sein können, daß sich an F angereicherte Glieder in relativ F-armer Umgebung bilden können, und daß OH-Glieder selten sind und nur unter Bildungsbedingungen niedriger Temperatur und weitgehender Abwesenheit von F auftreten.

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With 8 Figures     

Fluid-rock interaction in the Mo-bearing Nebelstein greisen complex,Bohemian Massif (Austria)

Summary In the Nebelstein area, molybdenite-bearing greisens occur together with peraluminous leucogranites. In the compositional change of the granites to the greisens, there is an almost complete loss of Na, combined with a decrease in Ca, Mg, Sr, and Ti concentrations. The progressive alteration is reflected by lower homogenization temperatures and increasing salinity in aqueous fluid inclusions. The fluid regime prior to greisenization was water-dominated with low salt contents, while the early stage of the greisen development was characterized by a mixed fluid containing carbon dioxide and water. This was succeeded by a moderate saline aqueous fluid which caused the mineralization by exchange of metal ions for Na⁺(Ca²⁺, K⁺). A negative correlation between salt content in fluid inclusions and Na₂O concentrations in the bulk rocks supports this model. Mass balance calculations for this interaction yield a minimum fluid-rock ratio of approximately 2 : I. Greisenization took place at a minimum pressure of 180 MPa (1.8 kb) and in a temperature range between 200 and < 400 °C.

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Fluid-Gestein-Wechselwirkung in dem Molybdänit führenden Greisenkomplex Nebelstein, Böhmische Masse (Österreich)

Zusammenfassung Die Molybdänglanz führenden Greisengesteine des Nebelsteins sind an peraluminöse Granite gebunden. Bei der Alteration der Granite ist für den Übergang Biotitgranit zu Greisen eine weitestgehende Verarmung an Na zu beobachten, gleichzeitig nehmen auch die Gehalte an Ca, Mg, Sr und Ti ab. Die fortschreitende Greisenbildung dokumentiert sich in den wäßrigen Flüssigkeitseinschlüssen durch steigende Salinität bei sinkenden Homogenisierungstemperaturen. Die fluide Phase war vor der Greisenbildung H₂O dominiert und niedrig salinar. Der Beginn der Alterationsprozesse ist durch CO₂ und H₂O hältige Fluide gekennzeichnet. Danach folgt ein Anstieg der Salinität, der auf den Austausch von Metallchloridlösungen gegen Na⁺, K^- und Ca^2- zurückgeführt wird. Dies läßt sich durch eine negative Korrelation der Salinität in den Flüssigkeitseinschlüssen mit dem Na-Gehalt der Gesteine belegen. Daraus wurde die Volumsbeziehung der den Granit durchströmenden fluiden Phase relativ zum Gestein mit mindestens 2 : 1 abgeleitet. Die Mineralisation fand bei einem Minimaldruck von 1,8 kb in einem Temperaturbereich von 200 - < 400 °C statt.

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This paper was presented at the IGCP 291 Project Symposium Metamorphic Fluids and Mineral Deposits, ETH Zürich, March21–23,1991.