In situ bioremediation of 1,2-dichloroethane under anaerobic conditions

Historic spillages of chlorinated hydrocarbons at a vinyl chloride plant in the Rotterdam–Botlek area in The Netherlands has lead to deep-seated pollution of the underlying aquifer. The principal pollutant is 1,2-dichloroethane (1,2-DCA). As a temporary measure, the contamination is being contained using a pump and treat system. In the long term, in-situ bioremediation has been proposed using a biologically active zone where pollutants would be dechlorinated by microorganisms that simultaneously degrade other carbon sources. In order to investigate the suitability of this new technology, a programme of laboratory tests was carried out. The laboratory programme involved a series of anaerobic soil column tests, where the selection and delivery of different carbon substrates that stimulated 1,2-DCA dechlorination were investigated. The soil columns were prepared using soil and groundwater samples from boreholes. Groundwater was flushed through the columns under anaerobic conditions. A comparison was made between the transformation of 1,2-DCA without a carbon substrate and in the presence of sugars (molasses) and alcohol (methanol) respectively. In addition, different modes of delivery were investigated. In the case of molasses, the material was injected into the column as a plug to simulate grout injection in the field, whereas methanol was delivered as a constant flow dissolved in the influent. Both carbon substrates resulted in the biotransformation of 1,2-DCA. However, fermentation of molasses produced secondary effects that led to a drop in pH and an excessive production of carbon dioxide, which temporarily blocked the flow of groundwater.     

Volatile-induced transport of HFSE, REE, Th and U in arc magmas: evidence from zirconolite-bearing vesicles in potassic lavas of Lewotolo volcano (Indonesia)

Potassium-rich calc-alkaline lavas of Lewotolo volcano, situated in the East Sunda Arc, Indonesia, contain the rare mineral zirconolite (CaZrTi₂O₇). Samples in which tiny grains of this mineral (3–25 μm in size) were found span the entire range of lava compositions (47–62 wt% SiO₂). To the best of our knowledge, this is the first record of primary zirconolite in juvenile arc volcanics. The mineral forms part of a vesicle-filling assemblage consisting of a network of quenched feldspar crystals and an SiO₂ phase, probably cristobalite. High contents of Th, U and REE (up to 9.3, 4.3 and 15.6 wt% oxide respectively) and very high Fe contents (up to 13.5 wt% Fe₂O₃) distinguish these zirconolites from those of other rock types. The extraction of volatile-rich phases with changing compositions in successive stages is considered to be responsible for the zirconolite formation. We hypothesise that a fluid capable of transporting HFSE, REE, Th and U was extracted from the magma and (partly) crystallised within voids which had formed earlier upon saturation of an aqueous fluid. Assuming that zirconolite compositions largely reflect trace metal contents of the coexisting fluid phase, significant amounts of `immobile' elements must have been transported on a macroscopic scale. Our findings thus point to a late-stage transfer of HFSE, REE, Th and U between different domains in a cooling magma body. Such a volatile-induced redistribution of trace elements at shallow levels of high-K volcanic systems may be significant for conventional geochemical modelling of magma evolution and for Th–U disequilibrium studies. Received: 3 November 1999 / Accepted: 29 February 2000     

Acidities of confined water in interlayer space of clay minerals

The acid chemistry of confined waters in smectite interlayers have been investigated with first principles molecular dynamics (FPMD) simulations. Aiming at a systematic picture, we establish the model systems to take account of the three possible controlling factors: layer charge densities (0 e, 0.5 e and 1.0 e per cell), layer charge locations (tetrahedral and octahedral) and interlayer counterions (Na⁺ and Mg²⁺). For all models, the interlayer structures are characterized in detail. Na⁺ and Mg²⁺ show significantly different hydration characteristics: Mg²⁺ forms a rigid octahedral hydration shell and resides around the midplane, whereas Na⁺ binds to a basal oxygen atom and forms a very flexible hydration shell, which consists of five waters on average and shows very fast water exchanges. The method of constraint is employed to enforce the water dissociation reactions and the thermodynamic integration approach is used to derive the free-energy values and the acidity constants. Based on the simulations, the following points have been gained. (1) The layer charge is found to be the direct origin of water acidity enhancement in smectites because the neutral pore almost does not have influences on water dissociations but all charged pores do. (2) With a moderate charge density of 0.5 e per cell, the interlayer water shows a pKa value around 11.5. While increasing layer charge density to 1.0 e, no obvious difference is found for the free water molecules. Since 1.0 e is at the upper limit of smectites’ layer charge, it is proposed that the calculated acidity of free water in octahedrally substituted Mg²⁺-smectite, 11.3, can be taken as the lower limit of acidities of free waters. (3) In octahedrally and tetrahedrally substituted models, the bound waters of Mg²⁺ show very low pKa values: 10.1 vs 10.4. This evidences that smectites can also promote the dissociations of the coordinated waters of metal cations. The comparison between the two Mg²⁺-smectites reveals that different layer charge locations do not lead to obvious differences for bound and free water acidities.     

Elevated marine deposits in Bermuda record a late Quaternary megatsunami

Deposits of coral-bearing, marine shell conglomerate exposed at elevations higher than 20 m above present-day mean sea level (MSL) in Bermuda and the Bahamas have previously been interpreted as relict intertidal deposits formed during marine isotope stage (MIS) 11, ca. 360–420 ka before present. On the strength of this evidence, a sea level highstand more than 20 m higher than present-day MSL was inferred for the MIS 11 interglacial, despite a lack of clear supporting evidence in the oxygen-isotope records of deep-sea sediment cores. We have critically re-examined the elevated marine deposits in Bermuda, and find their geological setting, sedimentary relations, and microfaunal assemblages to be inconsistent with intertidal deposition over an extended period. Rather, these deposits, which comprise a poorly sorted mixture of reef, lagoon and shoreline sediments, appear to have been carried tens of meters inside karst caves, presumably by large waves, at some time earlier than ca. 310–360 ka before present (MIS 9–11). We hypothesize that these deposits are the result of a large tsunami during the mid-Pleistocene, in which Bermuda was impacted by a wave set that carried sediments from the surrounding reef platform and nearshore waters over the eolianite atoll. Likely causes for such a megatsunami are the flank collapse of an Atlantic island volcano, such as the roughly synchronous Julan or Orotava submarine landslides in the Canary Islands, or a giant submarine landslide on the Atlantic continental margin.     

Post-Svecokarelian andinotype evolution in central Sweden

Granitoids and associated volcanics, postorogenic in relation to the Svecokarelian orogeny, constitute a belt in central Sweden. Evidence presented in this paper suggest that the belt originated in an Andinotype orogenic environment. The inferred development of the belt was characterized by fracture-controlled high-level emplacement of batholiths in an ensialic setting. Voluminous venting of ignimbrites and formation of grabens through cauldron subsidence accompanied the recurrent intrusive activity. Block movements and episodes of burial metamorphism appear to have been prominent features throughout the history of the post-Svecokarelian belt.

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Zusammenfassung Granitoide Plutonite und verwandte Vulkanite, post-orogen im Verhältnis zur Svekokarelischen Orogenese, bilden einen Gürtel in Mittelschweden. Es wird gezeigt, daß der Gürtel in einer andinotypen Orogenese gebildet wurde. Die vorgeschlagene Entwicklung des Gürtels ist geprägt durch spaltentektonisch kontrollierte Platznahme von Batholithen in einem seichten Niveau der Kruste in ensialischem Mileau. Umfangreiche Eruptionen von Ignimbriten sowie die Bildung von Grabenbrüchen durch Kalderen-Einstürzungen begleiten die erneute intrusive Tätigkeit. Blockbewegungen und episodische Versenkungsmetamorphosen sind charakteristisch während der gesamten Entwicklungsgeschichte des post-svekokarelischen Gürtels.

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Résumé Des granitoïdes et des volcanites associées, postorogéniques par rapport à l'orogénese svécokarélienne, forment une ceinture en Suède centrale. La présente étude suggère que la mise en place de ces roches s'est effectuée dans un environment orogénique Andinotype. L'évolution de la ceinture c'est caractérisée par la mise en place; contrée par des fractures, de batholites peu profonds, en milieu ensialique. Des volumineuses éruptions d'ignimbrites et la formation de grabens par «cauldron subsidence» ont accompagné la mise en place des batholites. Des mouvements verticaux de blocs, ainsi que des épisodes de métamorphisme d'enfouissement («burial metamorphism») semblent être des faits dominants du développement historique de la ceinture post-svécokarélienne.

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The Ordovician chondrite from Brunflo, central Sweden: III. Geochemistry of terrestrial alteration

The fossil H chondrite Brunflo, found in a slab of Ordovician limestone from central Sweden, is pervasively altered to an assemblage dominated by calcite and barite. The meteorite is surrounded by a 15–20 cm wide zone of lighter colors than the unaffected limestone due to dissolution of hematite. Here we present detailed geochemical analyses of two meteorite samples, 14 limestone samples at distances from 0 to 29 cm along two profiles from the meteorite, and a reference sample of Brunflo limestone. Element concentrations in Brunflo and surrounding bleached limestone have been strongly disturbed during two stages of alteration (early oxygenated and deep burial). In the meteorite, the Ni/Co ratio has changed from an initial value of 20 to 0.8 and redox sensitive elements like V, As, Mo, Re and U are strongly enriched. The sulfur isotope composition of barite from Brunflo (δ³⁴S=+35‰) indicates initial loss of meteoritic sulfide, followed by later accumulation of sea water sulfate as barite. During deep burial under more reducing conditions, reduction processes supported by an externally derived reductant possibly derived from alum shale underlying the limestone, were largely responsible for the observed redox phenomena. In spite of massive redistribution of many elements, concentrations of Pt, Ir and Au remain at chondritic levels. The geochemistry and mineralogy of alteration determined for Brunflo are similar to those in “reduction spots” in red beds, where accumulation of a similar suite of elements (except Mo, Re) occurred as a result of isolated reduction activity.     

High-speed photography of the bubble generated by an airgun1

High-speed photography has been used visually to study the shape, surface, turbulence and behaviour of an underwater oscillating bubble generated by an airgun. The source was a BOLT airgun with a chamber volume of 1.6cu.in., placed in a 0.85m³ tank at 0.5m depth. Near-field signatures were also recorded in order to compare the instant photographs of the oscillating bubble with the pressure field recorded about 25 cm from the gun. Estimations of the bubble-wall velocity and bubble radius estimated from high-speed film sequences are also presented, and are compared with modelled results. The deviation between the modelled and measured bubble radii was at most 9%. In order to check the capacity for transmission of light through the bubble, a concentrated laser beam was used as illumination. We found that the air bubble is a strong scattering medium of laser light, hence the bubble is opaque.     

Initial uncertainties in ‘nuclear winter’: A proposed test based on the dresden firestorm

Conclusions An extinction optical depth of 20 is necessary for total darkness (NAS, 1985), although a considerably lower value than that can produce near-total darkness because scattered light does not generate shadows and contrast. It can be seen that the Dresden firestorm smoke cloud, calculated under the conditions usually assumed in nuclear winter calculations, should have resulted in total darkness over a vast area.Using the 500 mb chart, it can be retrodicted that the smoke plume, as part of the counterclockwise circulation about the low over southern Sweden, was over central Poland as dawn broke on the 14th. Indeed, at 9 AM (Table I), smoke from what had been Dresden should have been passing over what had been Warsaw. Depending upon the specific size of the plume at the time, anywhere from a few hundred thousand to over ten million people should have been plunged into darkness.It appears unlikely that such extensive darkening could have gone unreported (especially in the light of the heightened awareness resulting from wartime conditions, and the proximity of the Soviet/German front). This has direct implications for the aforementioned initial uncertainties in nuclear winter. Possible explanations include: (a) Very low smoke emission factors - perhaps even lower than 0.001 (Broyles, 1985); (b) Substantial removal of smoke in the black rain that followed the firestorm (Irving, 1963, p. 175). Values for prompt smoke removal reaching 90% are not out of the realm of possibility (Schneider et al., 1986; Penner, 1986).The present author is of the opinion that more effort should be expended by students of the nuclear winter phenomenon to learn from WWII mass urban fires. Many eyewitnesses to these events must still be living, and there must be at least some scientifically-useable material in archives. For example, there is a 122-m, 10-min motion film of the Dresden firestorm (Irving, 1963, p. 159). It is in the film archives of the Imperial War Museum. Perhaps some new details of firestorm genesis, spread, etc. could be learned from it. There must be other log books, such as the one of Kraus (1986), which could well yield scientificallyvaluable information.