Sources and sinks of sea salt in a newfoundland blanket bog

Over an oceanic peatland, the concentration of Na in fog averaged 38.1 mgl^?1 compared with 1.8 mgl^?1 in rain, resulting in a significant flux of mineral elements to the surface. Between 16 May and 20 June 1990 the average mass flux of Na to the bog surface by fog, rain, and dry deposition was 21.9, 10.4 and 7.0 mg m^?2 d^?1. There was little long-term storage of Na within the peatland system, where Na losses measured in stream runoff averaged 34.8 mg m² d^?1, and deep groundwater losses 4 mg m^?2 d^?1. Calcium and Mg were preferentially retained in the organic soil, whereas K was relatively mobile. Potassium tended to become concentrated in the unsaturated zone. Stream runoff had a consistently higher pH than groundwater, corresponding to higher Ca and Mg concentrations, which may have been from mineral sources in the headwater ponds. Otherwise, the stream water chemistry was closely related to groundwater in the upper layers of the peat deposit.     

Detection of rovibrationally excited H2 formed through the heterogeneous recombination of H atoms on a cold HOPG surface

This paper reports results from an experiment designed to measure the nascent rovibrational population of H₂ molecules that have formed through the heterogeneous recombination of H atoms on the surface of cosmic dust analogues under conditions approaching those of the interstellar medium (ISM). H₂ that has formed on a highly oriented pyrolytic graphite (HOPG) surface has been detected, using laser induced resonance-enhanced multi-photon ionization (REMPI), in the v = 1 (J= 0–3) rovibrational states at surface temperatures of 30 K and 50 K. These excited product molecules display rotational temperatures significantly higher than the target surface temperature. These first results suggest that a considerable proportion of the binding energy released on formation of the H₂ is deposited in the surface, in addition to internal excitation of the product molecules. This revised version was published online in July 2006 with corrections to the Cover Date.     

Offshore granulites from the Bay of Biscay margins: fission tracks constrain a Proterozoic to Tertiary thermal history

Zircon and apatite fission track ages were determined on granulites dredged along the Bay of Biscay margins. A sample from Ortegal Spur (Iberia margin) yielded 725 ± 67 Ma (zircon). A sample from Le Danois Bank (Iberia margin) yielded 284 ± 58 Ma (zircon), indicating post‐Variscan cooling. Apatite from this sample gave 52 ± 2 Ma, interpreted as final cooling after ‘Pyrenean’ thrust imbrication. Two other samples from Le Danois Bank have Early Cretaceous apatite ages (138 ± 7 and 120 ± 8 Ma), interpreted to result from exhumation during rifting. Finally, a granulite from Goban Spur (Armorican margin) gave 212 ± 10 Ma (apatite), coinciding with a precursory rifting phase. Together with published radiometric results, these data indicate a Precambrian high‐grade terrane at the site of the current margins. The distribution of the granulites on the seafloor reflects tectonic and erosional processes related to (a) Mesozoic rifting and (b) Early Tertiary incipient subduction of the Bay of Biscay beneath Iberia.     

Detailed <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating of geologic events associated with the Mantos Blancos copper deposit,northern Chile

The ⁴⁰Ar/³⁹Ar geochronological method was applied to date magmatic and hydrothermal alteration events in the Mantos Blancos mining district in the Coastal Cordillera of northern Chile, allowing the distinction of two separate mineralization events. The Late Jurassic Mantos Blancos orebody, hosted in Jurassic volcanic rocks, is a magmatic-hydrothermal breccia-style Cu deposit. Two superimposed mineralization events have been recently proposed. The first event is accompanied by a phyllic hydrothermal alteration affecting a rhyolitic dome. The second mineralization event is related to the intrusion of bimodal stocks and sills inside the deposit. Because of the superposition of several magmatic and hydrothermal events, the obtained ⁴⁰Ar/³⁹Ar age data are complex; however, with a careful interpretation of the age spectra, it is possible to detect complex histories of successive emplacement, alteration, mineralization, and thermal resetting. The extrusion of Jurassic basic to intermediate volcanic rocks of the La Negra Formation is dated at 156.3 ± 1.4 Ma (2σ) using plagioclase from an andesitic lava flow. The first mineralization event and associated phyllic alteration affecting the rhyolitic dome occurred around 155–156 Ma. A younger bimodal intrusive event, supposed to be equivalent to the bimodal stock and sill system inside the deposit, is probably responsible for the second mineralization event dated at ca. 142 Ma. Other low-temperature alteration events have been dated on sericitized plagioclase at ca. 145–146, 125, and 101 Ma. This is the first time that two distinct mineralization events have been documented from radiometric data for a copper deposit in the metallogenic belt of the Coastal Cordillera of northern Chile. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Intercomparison of coastal area morphodynamic models

Five different coastal area morphodynamic models have been set up to run on the same offshore breakwater layout and an intercomparison carried out on the hydrodynamic and morphodynamic output produced by each scheme. In addition, the predicted morphodynamics was checked against available laboratory and field data.It is concluded that the models are capable of producing realistic estimates for the dominant morphodynamic features associated with offshore breakwaters. Coupling of the wave, current and sediment transport components of each scheme is shown to yield bathymetry which attains a state of equilibrium, unlike models which are based on the initial transport field only.     

Geochemical variation in ferromanganese nodules and associated sediments from the Pacific Ocean

The major and minor element compositions of a suite of abyssal sea-floor ferromanganese nodules and associated sediments from the eastern central Pacific have been used to examine inter-element relationships and the mineralogy of the nodules, the relationship between the composition of nodules and their associated sediments and regional variations in composition with respect to likely modes of formation of such deposits. Apart from Mn and Fe, significant proportions of the total Ti, Ca, Mg, K, Ba, Sr, Th and Y and almost all the P, As, Ce, Co, Cu, Mo, Ni, Pb, Zn and Zr are present in the oxide fractions of the nodules. The Mg, Ba, Cu, Mo, Ni and Zn contents are significantly correlated with the Mn content, while Ti, P, As, Pb, Sr, Y and Zr are similarly correlated with the total Fe content.Nodules from the northeastern tropical Pacific have Mn/Fe ratios higher than those in the oxide fractions of their associated sediments, todorokite as the principal Mn phase and relatively high concentrations of minor elements associated with Mn. Nodules from the south central Pacific have Mn/Fe ratios similar to those in the oxide fractions of the associated sediments, δ-MnO₂ as the only Mn-phase, and relatively high concentrations of minor elements associated with Fe. There appears to be a smooth gradation in composition in the tropical Pacific between these two end members.The regional compositional variation is interpreted as a reflection of different sources of metals for, and different growth mechanisms of, sea-floor nodules. The oxide precipitate from sea water consists of δ-MnO₂, has a relatively low Mn/Fe ratio and minor element contents related to the total Fe and Mn(δ-MnO₂) content. The oxide precipitate forming in areas of very low sedimentation as a result of diagenetic remobilisation in the surface sediment consists of todorokite, and has a high Mn/Fe ratio and enhanced metal content in the Mn-(todorokite)phase. Available information on the morphology and compositional variation of individual nodules from the tropical Pacific corroborates these contrasting metal sources and suggests that they can be resolved on the scale of an individual oxide concretion.