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.     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

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.

     

Palaeoclimatic studies in South Shetland Islands,Antarctica, based on numerous stratigraphic variables in lake sediments

The hitherto longest found lake sediment sequence on Byers Peninsula, Livingston Island, South Shetland Islands, was analysed with respect to lithology, chronology, diatoms, Pediastrum, pollen and spores, mosses, mineralogy, and sediment chemistry. During the ca. 5000 year long development the sediments were influenced by frequent tephra fall-outs. This volcanic impact played a major role in the lake's history during two periods, 4700–4600 and 2800–2500 BP, but was of importance during the lake's entire history with considerable influence on many of the palaeoenvironmentally significant indicators. The large and complex data set was analysed and zonated with different types of multivariate analysis. This resulted in a subdivision of the sequence into 8 time periods and 21 variables. Redundancy analysis (RDA) of this data set, both without and with the tephra periods, and with 4–6 of the variables as explanatory environmental variables, reveal that climatic/environmental signals are detectable. The palaeoclimatic picture that emerged out of the tephra noise suggests that the first 100 years were characterized by mild, humid conditions. This was followed by a less mild and humid climate until ca. 4000 BP when a gradual warming seems to have started, coupled with increased humidity. These mild and humid conditions seem to have reached an optimum slightly after 3000 BP. At ca. 2500 BP a distinct climatic deterioration occurred with colder and drier conditions and long seasons with ice cover. This arid, cold phase probably reached its optimum conditions at ca. 1500 BP, when slightly warmer conditions might have prevailed for a while. Except for the modern sample with rather mild climate, the last 1400 years seem to have been fairly arid and cold, and the effects of the frequent volcanic activity during this period is only vaguely seen in the records.     

Passing through resonance: The excitation and dissipation of the lunar free libration in longitude

The acceleration of the mean lunar longitude has a small effect on the periods of most terms in a Fourier expansion of the longitude. There are several planetary perturbation terms that have small amplitudes, but whose periods are close to the resonant period of the lunar libration in longitude. Some of these terms are moving toward resonance, some are moving away from resonance, and the periods of those terms that do not include the Delaunay variables in their arguments are not moving. Because of its acceleration of longitude, the Moon is receding from the Earth, so the magnitude of the restoring torque that the Earth exerts on the rotating Moon is gradually attenuating; thus resonance itself is moving, but at a much slower rate than the periods of the accelerating planetary perturbations. There are five planetary perturbation terms from the ELP-2000 Ephemeris (with amplitudes of 0.00001 or greater) that have passed through resonance in the past two million years. One of them is of special interest because it appears to be the excitation source of a supposed free libration in longitude that has been detected by the lunar laser ranging experiment. The amplitude of the term is only 0.00021 but it could be the source of the 1 amplitude free libration term if the viscoelastic properties of the Moon are similar to those of the Earth.     

Generalized theory of impacts in particulate systems

The theory of collisional systems is generalized for an arbitrary geometry and forces acting in the system, mixtures of different particle types, friction, small deviations from the ideal spherical form, axial rotation, finite size of particles and gravitational interactions. Terms for the formation of new particles and destruction of old ones are also included, and other unspecified parameters can be introduced. Although some approximations are made to simplify the basic equations and to avoid excessive numerical interactions, a comparison with computer simulations shows a good agreement. The tests were continued up to the optical thickness = 5.     

Sulfide oxidation—an environmental problem within colliery spoil dumps

Because of the high degree of automation in the coal mining industry in the Ruhr area, Germany, about 1 metric ton of crushed rock/colliery spoil is brought to the surface for every metric ton of coal. Most of the colliery spoil disposed of must be dumped. These colliery spoil dumps are anthropogenic geological sediment bodies, which have a characteristic facies resulting from geological, technical, and economical factors connected with the formation of the dumps. The relation between the facies of the dumps and these factors, for example, is examplified with the pyrite content within the colliery spoil. Pyrite content within the dumps is dependent both on the conditions during sedimentation and (early) diagenesis and the techniques used for mining and processing. Thus, this geologic-technical facies of the dumps controls the weathering processes on and in dumps. These humaninduced processes are mainly responsible for the environmental impact on soil and groundwater. Oxidation of pyrite as well as alteration of pyrite under anoxic conditions yields dissolution of carbonates, accompanied by gypsum formation, by acid attack and strong acidification takes place.     

Fluid inclusions in upper mantle xenoliths from Northern Patagonia,Argentina: Evidence for an upper mantle diapir

Summary Three generations of fluid inclusions can be recognized in upper mantle xenoliths from alkali basalts of the Somoncura Massif, Northern Patagonia, Argentina. The first (early, primary) one consists of dense CO₂ inclusions which were trapped in the mantle-crust boundary zone (22–36 km minimum trapping depth). Their co-genetic relationship with silicate melt inclusions enables us to constrain their minimum trapping temperature at 1200°C, indicating a high temperature event in a cooler environment. The late (pseudosecondary and secondary) generations of fluid inclusions were classified in accordance with their homogenization temperature to liquid CO₂ (L1) and vapor CO₂ (L2) phase. The minimum trapping depth for the first of the late inclusions (L1) is about 16 km. In spite of the uncertainties related to this value, L1 inclusions indicate that the upper mantle rocks, of which samples were delivered by the basalts, had some residence time in the middle crust where they experienced a metasomatic event. The fact that this event did not destroy the earlier inclusions, places severe constraints on its duration. The second late inclusions (L2) are low-pressure CO₂ inclusions with a minimum trapping depth of only 2 km, presumably a shallow magma chamber of the host basalts. The succession of fluid inclusions strongly points toward a fairly fast uprising upper mantle underneath Northern Patagonia. The petrology and mineral chemistry of the peridotitic xenoliths support this view. Extensive partial melting and loss of these melts is indicated by the preponderance of harzburgites in the upper mantle underneath Northern Patagonia, a fairly unusual feature for a continental upper mantle. That depletion event as well as several metasomatic events — including those which left traces of fluid inclusions — are possibly related to a high-speed diapiric uprise of the upper mantle in this area. The path can be traced from the garnet peridotite stability field into the middle crust, a journey which must have been unusually fast. Differences in rock, mineral, and fluid inclusion properties between geographic locations suggest a diffuse and differential type of diapirism. Future studies will hopefully help to map the full extent and the highs and lows of this diapir and elucidate questions related to its origin and future.

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Fluid-Einschlüsse in Erdmantel-Xenolithen von Nord-Patagonien: Evidenz für einen Diapir im oberen Erdmantel

Zusammenfassung Erdmantel - Xenolithe in Alkali-Basalten des Somoncure Massivs, Nord-Patagonien, Argentinien, führen drei Generationen von Fluid-Einschlüssen. Die erste (frühe, primäre) Generation besteht aus dichten CO₂-Einschlüssen, welche offenbar in der Mantel-Kruste Grenzzone (22–36 km Minimum-Tiefe) eingeschlossen wurden. CO₂-Einschlüsse sind kogenetisch mit Silikat-Schmelzeinschlüssen. Dies erlaubt die Abschätzung der Einschließ-Temperatur mit minimal 1200°C, was auf ein Hochtemperatur-Ereignis in einer deutlich kühleren Umgebung hinweist. Die späten (pseudosekundäre und sekundäre) CO₂- Fluid-Einschlüsse bilden zwei Generationen von denen die eine in die flüssige (L1), die andere in die Dampfphase (L2) homogenisieren. Die minimale Einschließ-Tiefe für die L1 Generation ist etwa 16 km. Dies bedeutet - auch bei Berücksichtigung der mit diesem Wert verbundenen Ungenauigkeit - daß diese Erdmantel-Gesteine einige Zeit in der mittleren Erdkruste verbrachten und ein metasomatisches Ereignis erlebten, bevor sie von den Basalten zur Erdoberfläche gebracht wurden. Die Tatsache, daß dieses Ereignis die frühen Einschlüsse nicht zerstörte, kann nur bedeuten, daß es von kurzer Dauer war. Die L2-Generation besteht aus Niedrigdruck CO₂-Einschlüssen mit einer Minimum-Einschließtiefe von nur 2 km. Dies könnte in einer seichten Magmakammer des Wirt Basaltes geschehen sein.Die Abfolge von Fluid-Einschlüssen deutet auf einen relativ schnell aufsteigenden oberen Erdmantel unterhalb von Patagonien hin. Die Petrologie und Mineralchemie der peridotitischen Xenolithe unterstützen das. Die Vorherrschaft von Harzburgiten im Erdmantel unterhalb von Nord-Patagonien deutet auf umfangreiche Bildung partieller Schmelzen und deren Abfuhr hin — eine für einen kontinentalen Mantel ungewöhnliche Situation. Sowohl die Verarmungsereignisse, als auch die metasomatischen Veränderungen (einschließlich jene, welche Spuren in Form von Fluid Einschlüssen hinterließen) machen das Vorhandensein eines schnell aufsteigenden Daipirs im oberen Erdmantel dieser Gegend wahrscheinlich. Der Aufstieg kann vom Stabilitätsbereich der Granat-Peridotite bis in die mittlere Kruste verfolgt werden und muß daher relativ schnell erfolgt sein. Unterschiede in Gesteins-, Mineral und Fluid-Eigenschaften zwischen verschiedenen Lokalitäten legen einen diffusen und differenziellen Diapirismus nahe. Zukünftige Studien sollten es ermöglichen, das Gesamtausmaß und die unterschiedlichen Aufstiegshöhen des Diapirs zu kartieren und Hinweise auf seine Entstehung und zukünftige Entwicklung zu erhalten.

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With 5 Figures     

High-resolution sequence stratigraphy of the Lower Triassic ‘Buntsandstein’ in the Netherlands and northwestern Germany

Detailed log correlations of the largely fluvio-lacustrine Lower Triassic Buntsandstein (Late Permian-Early Anisian), carried out on 80 wells in the Dutch onshore and offshore areas, can be linked to northwest-German high-resolution sequence stratigraphy. The correlations show that cyclic sedimentation occurred in large parts of the basin. Seven 1st-order sequences are recognised, namely the Main Claystone, Rogenstein, Volpriehausen, Detfurth, Hardegsen, Solling and Lower Röt Sequences. They are overlain by the lower part of the Upper Röt–Lower Muschelkalk Sequence. Distinct sequence boundaries have been identified at the bases of four sequences: Volpriehausen, Detfurth, Solling and Upper Röt. The higher-order sequences consist of fining-upwards cycles with a thickness of up to tens of metres. The sequences are laterally persistent and have a characteristic expression on gamma-ray and sonic logs. In the Lower Buntsandstein, they display a uniform character throughout most of the area, with only minor differences in thickness or lithology. NNE-oriented lows and swells were formed during deposition of the Volpriehausen, Detfurth and Hardegsen Sequences. Uplift prior to the deposition of the Solling Sequence caused deep erosion on the swells in the basin and minor erosion in the lows. The high-resolution sequences probably represent alternating, relatively wet and dry climatic periods, with a periodicity of about 100 000 years. An analysis of the sequences suggests that their reduced thickness on the swells is mainly the effect of erosion. This is supported by analyses of the accumulation patterns and rates.