The isotopic ratios O/O and O/O in molecular oxygen and their significance in biogeochemistry

Recently, a new method has been introduced for the estimation of photosynthetic oxygen production from the triple isotope composition (δ¹⁷O and δ¹⁸O) of dissolved O₂ in the ocean and of air O₂ in ice cores. This method is based on the deviations (¹⁷Δ) from mass dependent respiratory fractionation, the major process affecting the isotopic composition of air O₂. To apply this method, the slope in the ¹⁷O/¹⁶O vs. ¹⁸O/¹⁶O relationship used for ¹⁷Δ calculation must be known with high accuracy. Using numerical simulations and closed system experiments, we show how the respiratory slope is manifested in the ¹⁷Δ of O₂ in situations where respiration is the only process affecting oxygen isotopic composition (kinetic slope), and in systems in steady state between photosynthesis and respiration (steady state slope). The slopes of the fractionation line in these two cases are different, and the reasons of this phenomenon are discussed. To determine the kinetic respiratory slope for the dominant O₂ consumers in aquatic systems, we have conducted new experiments using a wide range of organisms and conditions and obtained one universal value (0.5179 ± 0.0006) in ln(δ¹⁷O + 1) vs. ln(δ¹⁸O + 1) plots. It was also shown that the respiratory fractionations under light and dark are identical within experimental error. We discuss various marine situations and conclude that the kinetic slope 0.518 should be used for calculating ¹⁷Δ of dissolved O₂. In contrast, a steady state fractionation slope should be used in global mass balance calculations of triple isotope ratios of O₂ in air records of ice cores.     

The supergene origin of ruthenian hexaferrum in Ni‐laterites

For two decades, the nature of Fe‐rich, oxygen‐bearing, Ru–Os compounds found in the supergene environment has been debated. Ru–Os–Fe‐oxides and nano‐intergrowths of ruthenium with magnetite have been proposed. We applied FE‐SEM, EMPA, μ‐Raman spectroscopy and synchrotron tts‐μXRD to Ru–Os–Fe compounds recovered from Ni‐laterites from the Dominican Republic. The results demonstrate that a significant portion of Fe exists in a common structure with the Ru–Os alloy, that is, ruthenian hexaferrum. This mineral occurs both as nanoparticles and as micrometric patches within a matrix of Fe‐oxide(s). Our data suggest that supergene ruthenian hexaferrum with a (Ru_0.4(Os,Ir)_0.1Fe_0.5)_?1.0 stoichiometry represents the most advanced weathering product of primary laurite within Ni‐laterites from the Dominican Republic.     

Bismuth‐melt trails trapped in cassiterite–quartz veins

Native bismuth in the form of metallic melt has been considered instrumental to the formation of some metallic ore deposits via a mechanism dubbed the “Liquid Bismuth Collector Model.” Here, we provide petrographical documentation of trail‐forming, μm‐sized blebs of native bismuth in cassiterite–quartz veins from the Santa Bárbara greisen Sn deposit in the Rondônia tin province of northern Brazil. These inclusions suggest the trapping of a Bi melt that took place during vein formation, in a mechanism similar to the entrapment of fluid inclusions.     

Upper Cretaceous marine‐continental transition (Leonese Area,NW Spain) defined from integrated outcrop and seismic stratigraphy

The Upper Cretaceous succession of the Leonese Area (NW Spain) comprises mixed clastic and carbonate sediments. This succession is divided into two lithostratigraphic units, the Voznuevo Member and the Boñar Formation, which represent fluvial, shoreface, intertidal, subtidal and open‐shelf sedimentary environments. Regional seismic interpretation and sequence stratigraphic analysis have allowed the study of lateral and vertical changes in the sedimentary record and the definition of third‐order levels of stratigraphic cyclicity. On the basis of these data, the succession can be divided into two second‐order depositional sequences (DS‐1 and DS‐2), incorporating three system tracts in a lowstand to transgressive to highstand system tract succession (LST–TST–HST). These sequences are composed of fluvial systems at the base with palaeocurrents that flowed westward and south‐westward. The upper part of DS‐1 (Late Albian–Middle Turonian) shows evidence of intertidal to subtidal and offshore deposits. DS‐2 (Late Turonian–Campanian) comprises intertidal to subtidal, tidal flat, shallow marine and lacustrine deposits and interbedded fluvial deposits. Two regressive–transgressive cycles occurred in the area related to eustatic controls. The evolution of the basin can be explained by base‐level changes and associated shifts in depositional trends of successive retrogradational episodes. By using isobath and isopach maps, the main palaeogeographic features of DS‐1 and DS‐2 were constrained, namely coastline positions, the existence and orientation of corridors through which fluvial networks were channelled and the location of the main depocentres of the basin. Sedimentation on the Upper Cretaceous marine platform was mainly controlled by (i) oscillations of sea level and (ii) the orientation of Mesozoic faults, which induced sedimentation along depocentres. Copyright © 2013 John Wiley & Sons, Ltd.     

Provenance of Holocene beach sand in the Western Iberian margin: the use of the Kolmogorov–Smirnov test for the deciphering of sediment recycling in a modern coastal system

Detrital zircons from Holocene beach sand and igneous zircons from the Cretaceous syenite forming Cape Sines (Western Iberian margin) were dated using laser ablation – inductively coupled plasma – mass spectrometry. The U–Pb ages obtained were used for comparison with previous radiometric data from Carboniferous greywacke, Pliocene–Pleistocene sand and Cretaceous syenite forming the sea cliff at Cape Sines and the contiguous coast. New U–Pb dating of igneous morphologically simple and complex zircons from the syenite of the Sines pluton suggests that the history of zircon crystallization was more extensive (ca 87 to 74 Ma), in contrast to the findings of previous geochronology studies (ca 76 to 74 Ma). The U–Pb ages obtained in Holocene sand revealed a wide interval, ranging from the Cretaceous to the Archean, with predominance of Cretaceous (37%), Palaeozoic (35%) and Neoproterozoic (19%) detrital‐zircon ages. The paucity of round to sub‐rounded grains seems to indicate a short transportation history for most of the Cretaceous zircons (ca 95 to 73 Ma) which are more abundant in the beach sand that was sampled south of Cape Sines. Comparative analysis using the Kolmogorov–Smirnov statistical method, analysing sub‐populations separately, suggests that the zircon populations of the Carboniferous and Cretaceous rocks forming the sea cliff were reproduced faithfully in Quaternary sand, indicating sediment recycling. The similarity of the pre‐Cretaceous ages (>ca 280 Ma) of detrital zircons found in Holocene sand, as compared with Carboniferous greywacke and Pliocene–Pleistocene sand, provides support for the hypothesis that detritus was reworked into the beach from older sedimentary rocks exposed along the sea cliff. The largest percentage of Cretaceous zircons (<ca 95 Ma) found in Holocene sand, as compared with Pliocene–Pleistocene sand (secondary recycled source), suggests that the Sines pluton was the one of the primary sources that became progressively more exposed to erosion during Quaternary uplift. This work highlights the application of the Kolmogorov–Smirnov method in comparison of zircon age populations used to identify provenance and sediment recycling in modern and ancient detrital sedimentary sequences.