The “Zero-order Model” revisited: Paul Schindler's influence on the development of trace metal scavenging models

In 1975 Paul Schindler produced the first oceanic trace metal scavenging model to explicitly include the role of surface chemistry as a control on trace metal water column residence times. The eighteen years that have elapsed since the publication of Schindler's seminal paper have seen the development of a variety of oceanic scavenging models; yet, the fundamental insight of his Zero-order Model remains the benchmark. This paper describes the role of Paul Schindler's work on surface chemistry in providing a framework for the current generation of trace element scavenging models.     

Synthetic zeolites formed from expanded perlite: Type,formation conditions and properties

Summary The starting material used was expanded perlite with a grain size < 40 m (74.5 wt.% SiO₂; 12.5 wt.% Al₂O₃). This material is a waste product obtained during the production of expanded perlite. The experiments were carried out with KOH solutions, mixtures of KOH and NaOH solutions (1:1) as well as NaOH solutions in the concentration range 0.5 N to 6.0 N at temperatures of between 100° and 140°C and with reaction periods of 2 hours to 13 days in closed system. In the experiments with KOH containing solutions zeolite ZK-19 (phillipsite), W (merlinoite), G (chabazite) and F (edingtonite) formed. Without addition of aluminium high percentages of zeolite ZK-19 (80–100 wt.%) and zeolite W (90–100 wt.%) were obtained. The addition of aluminium rendered possibly the formation of 90 to 100 wt.% of zeolite G and 85 to 100 wt.% of zeolite F, respectively. In the experiments with NaOH solutions analcime, zeolite Na-Pc (gismondine), zeolite HS (sodalite hydrate) and zeolite A formed. High percentages of zeolite Na-Pc (90–100 wt.%), zeolite HS (up to 100 wt.%) and analcime (up to 100 wt.%) were synthesized without addition of aluminium. The formation of high percentages of zeolite A (95–100 wt.%), however, needs the addition of aluminium, NaCI and seed crystals. The temperature stability of the zeolites decreases in the following sequence: K-F > K-W K-ZK-19 (Na), K-W Na, K-F G_si-rich (Na), K-ZK-19 >> Na-Pc G_si-poor. Zeolite A has a very good temperature stability up to temperatures of } 550 °C similar to that of zeolite K-W. At higher temperatures, however, its stability is very poor. The NH₄ ⁺-exchange capacities (meq/g) of the different zeolites amount to the following values: ZK-19:2.8 - 3.2; W:3.0 - 3.2; G:2.3 - 3.6; A:3.1 - 3.2; Na-Pc:3.5 - 3.6; F : 3.9 - 4.8.

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Zeolithsynthese aus Blähperlit—Art, Bildungsbedingungen und Eigenschaften

Zusammenfassung Ausgangsmaterial der experimentellen Untersuchungen war Blähperlit mit einer Korngröße < 40 ,m (74,5 Gew.-% SiO₂; 12,5 Gew.-% Al₂O₃). Dieses Material ist ein Abfallprodukt, das bei der Produktion von Blähperlit anfällt. Die Experimente wurden mit KOH-Lösungen, Lösungsgemischen aus KOH und NaOH (1:1) sowie mit NaOH-Losungen im Konzentrationsbereich 0,5 n-6,0 n bei Temperaturen von 100° – 140°C und über Reaktionszeiten von 2 Stunden bis zu 13 Tagen im geschlossenen System durchgeführt. In den Experimenten mit KOH-hältigen Lösungen bildeten sich die Zeolithe ZK-19 (Phillipsit), W (Merlinoit), G (Chabasit) und F (Edingtonit). Hohe Prozentgehalte an Zeolith ZK-19 (80 – 100 Gew.-%) und Zeolith W (90–100 Gew.-%) entstehen nur ohne Zugabe von Aluminium. Die Bildung von 90–100 Gew.-% Zeolith G bzw. 85–100 Gew. % Zeolith F ist dagegen durch die Zugabe von Aluminium möglich. In den Experimenten mit NaOH-Lösungen bildeten sich die Zeolithe Analcim, Na-Pc (Gismondin), HS (Sodalithhydrat) und Zeolith A. Hohe Prozentanteile an Zeolith Na-Pc (90–100 Gew.-%), HS (bis zu 100 Gew. %) und Analcim (bis zu 100 Gew.-%) wurden ohne Aluminium-Zugabe synthetisiert. Die Bildung von hohen Gehalten an Zeolith A (95–100 Gew. %) ist jedoch nur unter Zugabe von Aluminium, NaCl und Kristallkeimen möglich.Die Temperaturbeständigkeit der Zeolithe nimmt in der folgenden Reihenfolge ab: K-F > K-W - K-ZK-19 (Na), K-W Na, K-F G_si-reich (Na), K-ZK-19 >> Na-Pc G_si-am. Zeolith A weist bis zu Temperaturen von etwa 550°C eine gute Temperaturbeständigkeit auf, die in etwa der von Zeolith K-W entspricht. Bei höheren Temperaturen ist die Beständigkeit jedoch sehr gering.Die NH⁴⁺-Austauschkapazitäten (mÄqu/g) der verschiedenen Zeolithe erreichen folgende Werte: ZK-19:2,8 - 3,2; W:3,0 - 3,2; G:2,3 - 3,6; A:3,1 - 3,2; Na-Pc:3,5 -3,6; F:3,9 - 4,8.

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With 2 Figures     

Corona textures in Proterozoic olivine melanorites of the Equeefa Suite,Natal Metamorphic Province,South Africa

Summary Olivine-plagioclase and phlogopite-plagioclase coronas have been identified from olivine melanorites of the Mid- to Late Proterozoic Equeefa Suite in southern Natal, South Africa. Olivine, in contact with plagioclase, is mantled by a shell of clear orthopyroxene, in turn rimmed by pale green (pargasitic) clinoamphibole. Locally a third rim, composed of a fine pargasite-spinel symplectite is developed adjacent to the plagioclase. The second corona reaction has produced greenish-brown pargasite at phlogopite-plagioclase interfaces. A third, less obvious reaction, between olivine and phlogopite is also noted. Analytical data of all the mineral phases present, along with the coronas, are given. Two-pyroxene thermometry yields magmatic core temperatures ( 1120°C), with rim compositions indicating equilibration at 850°C. Consistent with this, the modelled olivine-plagioclase reaction occurs between 830–1050°C with a_waterbetween 0.1 and 1.0 at 7 kbar. The three reactions took place during a prolonged history of cooling and partial hydration of the magmatic olivine melanorites from over 1000°C down to 600°C. The P-T conditions indicated by the reactions suggest this cooling process was essentially isobaric, indicating that the area was not subjected to rapid uplift or burial throughout this entire period.

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Korona-Texturen in proterozoischen Olivin-Melanoriten der Equeefa Suite, Natal Metamorphic Province, Südafrika

Zusammenfassung Aus Olivin-Melanoriten der mittel- bis spätproterozoischen Equeefa Suite im südlichen Natal, Südafrika, wurden Olivin-Plagioklas und Phlogopit-Plagioklas-Koronartexturen beobachtet. Olivin, der mit Plagioklas im Kontakt steht, wird von einem klaren Saum vom Orthopyroxen ummantelt, der seinerseits von blaßgrünem (pargasitischem) Klinoamphibol umsäumt wird. Stellenweise ist ein dritter Saum, bestehend aus feinkörnigem symplektitischem Pargasit-Spinell im Kontakt mit Plagioklas ausgebildet. Die zweite koronabildende Reaktion resultiert in Bildung eines grünbraunen Pargasites an Phlogopit-Plagioklas Kornkontakten. Eine dritte, weniger auffällige Reaktion zwischen Olivin und Phlogopit wurde ebenfalls beobachtet. Zwei-Pyroxen-Thermometrie ergab magmatische Temperaturen der Kernbereiche ( 1120°C) und belegt eine Gleichgewichtseinstellung in den Randzonen bei ca. 850°C. Olivin-Plagioklas-Modellreaktionen liegen ebenfalls in einem Temperaturbereich von 830–1050°C bei Wasseraktivitäten von 0.1 bis 1.0 und einem Druck von 7 kbar. Die drei Reaktionen liefen im Zuge einer länger andauernden Abkühlung unter teilweiser Hydratisierung der magmatischen Melanorite in einem Temperaturbereich von 1000°C bis ca. 600°C ab. Die aus den Reaktionen ableitbaren P-T-Bedingungen sprechen für eine im wesentlichen isobare Abkhlungsgeschichte und zeigen, daß dieses Gebiet wáhrend dieser gesamten Periode keiner raschen Hebung bzw. keiner Versenkung unterworfen worden ist.

     

An occurrence of ardennite in quartz veins in piemontite schist,Western Otago,New Zealand

Summary Ardennite of complex composition: (Mn²⁺ _3.488Ca_0.509Ba_0.002)₌₄(Mg_0.916916 Fe³⁺ _0.165 Mn³⁺ _0.099Cu_0.033Ni_0.009Zn_0.006 Ti_0.008Al_4.764)₌₆(As⁵⁺ _0.823V⁵⁺ _0.022P_0.005B_0.069Al_0.042Si_5.039)₌₆O_21.81(OH)_6.17 occurs in crack-seal quartz veins in quartz-albite-piemontite-spessartine-phengitehematite-chlorite-rutile-tourmaline ± calcite schist of the Haast Schist Group near Arrow Junction, western Otago, New Zealand. The Mn²⁺/Mn³⁺-ratio is sensitive to calculations and to accuracy of analyses. Boron is detected in ardennite for the first time. Other properties include = 1.734(3), = 1.735(3), = 1.751(3), 2V_Z = 30(2)°;a = 8.721(1),b = 5.816(1),c = 18.545(3) Å,V = 940.7(2) ų. Associated mineral phases are spessartine, hematite, piemontite containing 0.7% SrO and 0.06% PbO, and phengite. Later-stage vein minerals comprise chlorite, albite, and manganoan calcite which were deposited under less highly oxidizing conditions. Digenite with minor intergrown covellite occurs in small amount with manganoan calcite and quartz in a cross-cutting late-stage veina chalcopyrite and native copper occur in other late-stage veins. Arsenic and other components of the ardennite and associated minerals are derived from highly oxidized ferromanganese oxide- and hydroxide-bearing siliceous pelagic sediments that formed the protolith for the piemontite schist. The veins formed at a relatively early stage after metamorphism peaked in the chlorite zone of the greenschist facies under conditions that have been estimated at about 4.5 kbar, 390 °C.

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Vorkommen von Ardennit in Quarzgängen aus Piemontit-Schiefern, West-Otago, Neuseeland

Zusammenfassung Ardennit mit der Zusammensetzung (Mn²⁺ _3.488Ca_0.509Ba_0.002)₌₄(Mg_0.916Fe³⁺ _0.165Mn³⁺ _0.099Cu_0.033Ni_0.009Zn_0.006 Ti_0.008Al_4.764)₌₆(As⁵⁺ _0.823V⁵⁺ _0.022P_0.005B_0.069Al_0.042Si_5.039)₌₆O_21.81(OH)_6.17 tritt in Crack-seal-Quarzgängen in Quarz-Albit-Piemontit-Spessartin-Phengit-Hämatit-Chlorit-Rutil-Turmalin ± Calcit-Schiefern der Haast Schiefer-Gruppe nahe der Arrow Junction, West-Otago, Neuseeland, auf. Die Proportionen von Mn²⁺/Mn³⁺ hängen von der Kalkulation und der Genauigkeit der Analyse ab. Bor wird zum ersten Mal im Ardennit bestimmt. Andere Eigenschaften sind: = 1.734(3), = 1.735(3), = 1.751(3), 2Vz = 30(2)°; a = 8.721(1), b = 5.816(1), c = 18.545(3) Å, V = 940.7(2) Å3. Assoziierte Mineralphasen sind Spessartin, Hämatit, Piemontit, der 0.7% SrO und 0.06% PbO enthält und Phengit. Spät gebildete Gangmineralien, wie Chlorit, Albit und Mn-Calcit, sind unter geringer oxidierenden Bedingungen entstanden. Digenit mit etwas Covellin tritt in kleinen Mengen zusammen mit Mn-Calcit und Quartz in einem querschlägigen Gang auf, Chalcopyrit und gediegenes Kupfer kommen in anderen späten Gängen vor. Arsen und andere Komponenten des Ardennites and der assoziierten Minerale können von hochoxidierten, Fe-Mn-Oxid- und Hydroxyd-führenden, Sireichen, pelagischen Sedimenten hergeleitet werden, die das Ausgangsgestein für den Piemontit darstellen. Die Gänge wurden in einem relativ frühen Stadium, nach dem Metamorphosehöhepunkt, innerhalb der Chloritzone der Grünschiefer-Fazies, unter ungefähr 4.5 kbar und 390°C, gebildet.

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With 4 Figures     

Sea level and diagenesis: a case study on Pleistocene beaches,Whalebone Bay,Bermuda

Pleistocene fluctuations of sea level have left marine and aeolian limestones intercalated with glacial red soils on the Bermuda Carbonate Platform (Atlantic, 64°50W, 32°20N). Successive eustatic highstands of similar amplitude drowned the tectonically stable platform and piled up similar sets of sediments. Up to three Pleistocene beaches are stacked in shorelines sections. Post-depositional diagenetic histories of these beaches can be linked to repeated changes in sea level and pore waters.This paper presents field evidence and petrographic results (microscope, X-ray, cathodoluminescence, SEMEDAX) for the diagenetic histories of two superimposed Pleistocene beaches in Whalebone Bay, Bermuda North Shore. The younger beach was deposited during isotopic stage 5e, about 120 ka ago. The age of the older beach may be isotopic stage 9 or older.Diagenesis drastically altered the older beach before the stage 5e transgression. Primary high-Mg calcite (HMC) and aragonite were no longer present. Marine skeletal grains were instead leached or recrystallized to low-Mg calcite (LMC). Primary and secondary pore space were largely reduced by LMC cement. Lines of needle relics reminiscent of marine aragonite cement occur as inclusions within syntaxial rim cements around echinoderm grains, indicating that a marine influence had at least once interrupted this period of freshwater alteration. Finally, before the rocks became buried by the sediments of the younger beach, a crust of marine, bladed HMC cement was precipitated throughout the pore space.The younger beach consists of skeletal grains that are, apart from the effects of non-selective dissolution, essentially unaltered. The sediments are only weakly lithified by cryptocrystalline LMC showing an alveolar texture, tangential fibres and other features characteristic of calichification. A younger post-depositional marine influence is not recorded.These results suggest that, under favourable conditions, diagenetic processes can document sea-level fluctuations. The recorded fluctuations, however, are difficult to assess because even major sea-level highstands may not produce a diagenetic imprint. Correspondence to: R. Vollbrecht     

Tectonometamorphic evolution of the Bohemian Massif: evidence from high pressure metamorphic rocks

The Variscan orogenic belt, of which the Bohemian Massif is a part, is typically recognized for its characteristic low pressure, high temperature metamorphism and a large volume of granites. However, there are also bodies of high pressure rocks (eclogites, garnet peridotites and high pressure granulites) which are small in size but widely distributed throughtout the Massif. Initially the high pressure rocks were considered to be relicts of a much older orogenic event, but the increasing data derived from isotopic and geochronological investigations show that many of these rocks have Palaeozoic protoliths. Metamorphic ages from the high pressure rocks define no single event. Instead, a number of discrete clusters of ages are found between about 430 Ma and the time of the dominant low pressure event at around 320–330 Ma.Most of the eclogite and granulite facies rocks are assigned to allochthonous nappes that arrived close to the end of the low pressure event, but before final granite intrusion. The nappes contain a mixture of different units and the relationship between rocks with high pressure relicts and host gneisses with no apparent signs of deep burial is still problematic. Some of the high pressure rocks retain evidence of multiple stages of partial re-equilibration during uplift. Moreover, it can be shown in certain instances that host gneisses also endured a multistage metamorphic development but with a peak event convergent with one of the breakdown stages in the enclosed rocks with high pressure relicts. It thus appears that the nappe units are composite bodies probably formed during episodic intracrustal thrusting. Fluids derived from prograde dehydration reactions in the newly under thrusting slab are taken to be the catalysts that drove the partial re-equilibrations.On the scale of the whole Massif it can be seen within the units with high pressure relicts that the temperature at the peak recorded pressure and that during the breakdown are variable in different locations. It is interpreted that regional metamorphic gradients are preserved for given stages in the history and thus the present day dismembered nappe relicts are not too far removed from their original spatial distribution in an original coherent unit. From the temperature information alone it is highly probable that the refrigerating underthrusting slab was situated in the north-west. However, this north-west to south-east underthrusting probably represents the major 380–370 Ma event and is no guide to the final thrusting that emplaced the much thinned nappe pile with high pressure relicts.Granite genesis is attributed to the late stage stacking, during the final Himalayan-type collision stage, of thinned crust covered by young, water-rich, sediments — erosion products of the earlier orogenic stages. Regional metamorphism at shallow depths above the voluminous granites was followed by final nappe emplacement which rejuvenated the granite ascent in places. Correspondence to: P. J. O'Brien     

Paleohydrology and paleoclimate records in a saline prairie lake core: mineral,isotope and organic indicators

This pilot study examines the potential of obtaining a sedimentary record of paleoenvironmental/climatic/hydrologic conditions for saline Redberry Lake in southern Saskatchewan, Canada. The tools are mineralogy, stable isotopes and pigments. The upper meter of an offshore sediment core contains 10 to 20% by weight aragonite (CaCO₃), which apparently precipitated in the water column. The ¹⁸O and ¹³C of the bulk aragonite (corrected for content of detrital calcite) vary by 4 to 5. Enrichment in ¹⁸O in aragonite is significantly correlated with pigment concentrations (chlorophyll a, phaeophytin). The ¹⁸O and pigment data provide evidence for relatively dry and/or warm conditions and high limnetic productivity for the period 2500 to 1500 yrs B.P. After 1500 B.P., the climate was apparently similar to the present, with two episodes of relatively enhanced productivity, dryness and/or warmth, at around 1000 to 900 and 500 to 200 B.P. During the past century, Redberry Lake has decreased approximately 8 m in depth and its salinity has doubled. No clear sedimentary signal was observed in response to these recent hydrologic trends. These changes have not been associated with a significant climate trend in the region, but may have been induced by land use changes in the catchment.This publication is the third of a series of papers presented at the Conference on Sedimentary and Paleolimnological Records of Saline Lakes. This Conference was held August 13–16, 1991 at the University of Saskatchewan, Saskatoon, Canada. Dr. Evans is serving as Guest Editor for this series.     

Stability of outer planetary orbits around binary stars: A comparison of Hill's and Laplace's stability criteria

A comparison is made between the stability criteria of Hill and that of Laplace to determine the stability of outer planetary orbits encircling binary stars. The restricted, analytically determined results of Hill's method by Szebehely and co-workers and the general, numerically integrated results of Laplace's method by Graziani and Black are compared for varying values of the mass parameter =m ₂/(m ₁+m ₂). For 00.15, the closest orbit (lower limit of radius) an outer planet in a binary system can have and still remain stable is determined by Hill's stability criterion. For >0.15, the critical radius is determined by Laplace's stability criterion. It appears that the Graziani-Black stability criterion describes the critical orbit within a few percent for all values of .     

Asteroid motion near the 3 : 1 resonance

A mapping model is constructed to describe asteroid motion near the 3 : 1 mean motion resonance with Jupiter, in the plane. The topology of the phase space of this mapping coincides with that of the real system, which is considered to be the elliptic restricted three body problem with the Sun and Jupiter as primaries. This model is valid for all values of the eccentricity. This is achieved by the introduction of a correcting term to the averaged Hamiltonian which is valid for small values of the ecentricity.We start with a two dimensional mapping which represents the circular restricted three body problem. This provides the basic framework for the complete model, but cannot explain the generation of a gap in the distribution of the asteroids at this resonance. The next approximation is a four dimensional mapping, corresponding to the elliptic restricted problem. It is found that chaotic regions exist near the 3 : 1 resonance, due to the interaction between the two degrees of freedom, for initial conditions close to a critical curve of the circular model. As a consequence of the chaotic motion, the eccentricity of the asteroid jumps to high values and close encounters with Mars and even Earth may occur, thus generating a gap. It is found that the generation of chaos depends also on the phase (i.e. the angles andv) and as a consequence, there exist islands of ordered motion inside the sea of chaotic motion near the 3 : 1 resonance. Thus, the model of the elliptic restricted three body problem cannot explain completely the generation of a gap, although the density in the distribution of the asteroids will be much less than far from the resonance. Finally, we take into account the effect of the gravitational attraction of Saturn on Jupiter's orbit, and in particular the variation of the eccentricity and the argument of perihelion. This generates a mixing of the phases and as a consequence the whole phase space near the 3 : 1 resonance becomes chaotic. This chaotic zone is in good agreement with the observations.     

Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons: effect of ionization

In order to test the hypothesis of ionized polycyclic aromatic hydrocarbons (PAHs) as possible carriers of the UIR bands, we realized a computational exploration on selected PAHs of small dimension in order to identify which changes ionization would induce on their IR spectra. In this study we performed ab initio calculations of the spectra of neutral and positively ionized naphthalene, anthracene, and pyrene. The results are significantly important. The frequencies in the cations are slightly shifted with respect to the neutral species, but no general conclusion can be reached from the three molecules considered. By contrast, the relative intensities of most vibrations are strongly affected by ionization, leading to a much better agreement between the calculated CH/CC vibration intensity ratios and those deduced from observations.