The Urquiola oil spill,La Coruña,Spain: Case history and discussion of methods of control and clean-up

A massive oil spill affected approximately 215 km of coastline as a result of the grounding and subsequent explosion of the supertanker Urquiola at the entrance to the harbour at La Coruña, Spain, on 12 May 1976. A total of 99–100 000 tons of Persian Gulf crude oil was lost, most of which burned, but an estimated 25–30 000 tons washed ashore. Over 2000 tons of dispersants were applied to the oil at sea. Land-based clean-up and control methods were largely inadequate to combat the spread of oil, and were ineffective at preventing large scale environmental damage.     

Chemical and petrographic correlations among carbonaceous chondrites

Detailed study of the petrographic and chemical properties of carbonaceous chondrites shows that the four distinct petrographic subtypes may be related to one of two distinct chemical subdivisions. These subdivisions are recognized primarily by the relative abundances of the nonvolatile elements Si, Ca, Al, Ti, Cu and Fe. C1, C2 and C3(O) chondrites form one subdivision. Vigarano subtype chondrites form the other subdivision and include chondrites previously referred to as C2, C3 and C4. Normalized to silicon, the abundances of Ca, Al and Ti are relatively enriched in Vigarano subtype chondrites, whereas Fe and Cu are relatively more abundant in C1, C2 and C3(O) chondrites. Volatile elements tend to correlate with petrographic subtypes rather than with chemical subdivisions. The available data suggest that nonvolatile element chemical fractionation of carbonaceous chondrites into the two chemical subdivisions occurred before chondrule formation and that present textural and mineralogic properties and volatile element abundances can be attributed to variations in chondrule-producing and accretion processes.     

Calculation of hydrogen isotopic fractionations in biogeochemical systems

Hydrogen-isotopic data are often interpreted using mathematical approximations originally intended for other isotopes. One of the most common, apparent in literature over the last several decades, assumes that delta values of reactants and products are separated by a constant fractionation factor: δ_p = δ_r + ε_p/r. Because of the large fractionations that affect hydrogen isotopes, such approximations can lead to substantial errors. Here we review and develop general equations for isotopic mass balances that include the differential fractionation of each component in a mixture and discuss their use in three geochemical applications. For the fractionation of a single component, the reactant and product are related by δ_p = α_p/rδ_r + ε_p/r, where α and ε refer to the same fractionation. Regression of δ_p on δ_r should give equivalent fractionations based on the intercept and slope, but this has not generally been recognized in studies of D/H fractionation. In a mixture of two components, each of which is fractionated during mixing, there is no unique solution for the three unknown variables (two fractionation factors and the elemental mixing ratio of the two hydrogen sources). The flow of H from CH₄ and H₂O to bacterial lipids in the metabolism of Methylococcus capsulatus provides an example of such a case. Data and conclusions from an earlier study of that system (Sessions et al., 2002) are reexamined here. Several constraints on the variables are available based on plausible ranges for fractionation factors. A possible refinement to current experimental procedures is the measurement of three different isotopes, which would allow unique determination of all variables.     

Low-temperature, polysulfide reactions of conjugated ene carbonyls: A reaction model for the geologic origin of S-heterocycles

The theoretical basis for a type of reaction of sulfur-acceptor carbon molecules with donor catenated forms of sulfur is presented. The reactions between conjugated ene carbonyls as sulfur-acceptors and polysulfide as a sulfur donor are described. The scope of this reaction is broadened by demonstrating that the room-temperature action of polysulfide on dienones produces thiophenes. Evidence is given for the structure of 2-benzoyl-5-phenylthiophene, resulting from 1,5-diphenyl-2,4-pentadien-1-one, and 2-acetyl-5-phenylthiophene, resulting from 6-phenyl-3,5-hexadien-2-one. Evidence is also presented for the structure of 2,4-dibenzoyl-3,5-diphenylthiolane, the product resulting from the action of polysulfide on the mixture of benzaldehyde and acetophenone. The same thiolane is shown to result as the minor thiolane component when chalcone reacts with polysulfide in 80% water/20% ethanol. The major component is a known rearranged thiolane identified by its physical properties. The reactiol of chalcone and polysulfide in ethanol at 0 or 25°C results in thiolane formation as evidenced by the isolation of 2,4-dibenzoyl-3,5-diphenylthiolane. However, the reaction of the same two compounds in boiling methanol (65°C) results in a competitive hydrogenation of chalcone giving dihydrochalcone in addition to the formation of thiolane. The demonstration of the low-temperature reaction of polysulfide with conjugated ene carbonyls in the present work adds an additional pathway for possible formation of S-heterocycles in the geosphere.     

Geochemistry and SHRIMP U‐Pb Zircon Dating of Mafic Rocks North of Zunhua City,Eastern Hebei,North China Craton: Paleoproterozoic Gabbro rather than Neoarchean Ophiolite

Abundant mafic-ultramafic blocks and dikes occur in the area north of Zunhua City, eastern Hebei Province, and were previously suggested to be part of a late Archean ophiolitic assemblage. We employed SHRIMP zircon dating and a geochemical study on these mafic and surrounding rocks to test the ophiolite hypothesis. The SHRIMP data suggest that three metagabbro samples were metamorphosed at ～1.8 Ga. Numerous ～2.5 Ga zircons display strong oscillatory zoning, characteristic of zircons from granitoid rocks but not from gabbro, so we suggest that these are xenocrystic grains. The age of these xenocrystic zircons and their metamorpbic rims suggests that these mafic blocks formed in Paleoproterozoic. The surrounding gneiss of intermediate composition also contains 2.5 Ga zircons with oscillatory zoning and 1.8 Ga metamorphic rims. Fractionated REE patterns and Nb, Ta, Zr, Hf negative anomalies to variable extent were observed in the mafic blocks and surrounding rocks, also supporting a significant difference in the chemistry of ophiolitic rocks. Our data suggest that many mafic blocks in northern Zunhua are not part of a late Archean ophiolite complex but part of a tectonically dismembered Paleoproterozoic intrusive gabbro complex. This study shows that late Paleoproterozoic metamorphism occurred in the western part of eastern Hebei Province.     

Humic Substances as a Mediator for Microbially Catalyzed Metal Reduction

The potential for humic substances to serve as a terminal electron acceptor in microbial respiration and to function as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides was investigated. The Fe(III)-reducing microorganism Geobacter metallireducens conserved energy to support growth from electron transport to humics as evidenced by continued oxidation of acetate to carbon dioxide after as many as nine transfers in a medium with acetate as the electron donor and soil humic acids as the electron acceptor. Growth of G. metallireducens with poorly crystalline Fe(III) oxide as the electron acceptor was greatly stimulated by the addition of as little as 100 μM of the humics analog, anthraquinone-2,6-disulfonate. Other quinones investigated, including lawsone, menadione, and anthraquinone-2-sulfonate, also stimulated Fe(III) oxide reduction. A wide phylogenetic diversity of microorganisms capable of Fe(III) reduction were also able to transfer electrons to humics. Microorganisms which can not reduce Fe(III) could not reduce humics. Humics stimulated the reduction of structural Fe(III) in clay and the crystalline Fe(III) forms, goethite and hematite. These results demonstrate that electron shuttling between Fe(III)-reducing microorganisms and Fe(III) via humics not only accelerates the microbial reduction of poorly crystalline Fe(III) oxide, but also can facilitate the reduction of Fe(III) forms that are not typically reduced by microorganisms in the absence of humics. Addition of humic substances to enhance electron shuttling between Fe(III)-reducing microorganisms and Fe(III) oxides may be a useful strategy to stimulate the remediation of soils and sediments contaminated with organic or metal pollutants.     

Echo character of the East Brazilian continental margin and its relationship to sedimentary processes

The nature and regional distributions of various types of bottom echoes recorded on 3.5-kHz echograms from the East Brazilian continental margin (8–30°S) provide valuable information about sedimentary processes which have been active on a regional scale. The ten types of echoes observed fall into two major classes: distinct and indistinct. Indistinct echoes have two sub-classes; prolonged and hyperbolic. A qualitative correlation is observed between three types of distinct and indistinct-prolonged echoes and the relative abundance of coarse, bedded sediment (silt, sand, gravel) in piston cores. Regions returning distinct echoes with continuous parallel sub-bottoms contain little or no coarse sediment; regions returning indistinct very prolonged echoes with no sub-bottoms contain very high concentrations of coarse sediment; and regions returning indistinct semiprolonged echoes with intermittent sub-bottoms contain moderate or intermediate amounts of coarse sediment. Thus the regional distributions of these three echo types reflect the dispersal of coarse terrigenous sediment throughout the region. High concentrations of coarse sediment are restricted to relatively small areas which are generally proximal to large deep-sea channels, whereas very low concentrations occur in distal regions such as the lowermost continental rise and adjacent abyssal plain. Moderate concentrations of coarse sediment occur throughout most of the continental rise. Five of the six types of hyperbolic echoes observed are reflected from erosional/depositional bed forms. Although some of these bed forms (especially on the upper continental rise) have probably been produced by gravity-controlled mass flows (turbidity currents, slumps, etc.) the fact that the most extensive and widespread regions of hyperbolic echoes occur in distal regions beneath the present axis of flow of the Antarctic Bottom Water suggests that most of these bed forms are the result of sediment reworking by the contour-following bottom currents of this water mass.