A new series of steryl chlorin esters: pheophorbide a steryl esters in an oxic surface sediment

Investigation of chlorins in the oxic surface sediment of a small eutrophic alpine lake (Motte lake) revealed the presence of a new series of steryl chlorin esters containing the pheophorbide a nucleus, together with their pyropheophorbide a steryl ester counterparts previously observed in the anoxic surface sediment of the same lake. Identification of the pheophorbide a steryl esters was based on comparison of spectroscopic, chromatographic and mass spectrometric characteristics of the compounds with those of a synthetic standard and of pyropheophorbide a steryl esters. Combined liquid chromatography-mass spectrometry analysis confirmed the absence of pheophorbide a steryl esters in the anoxic sediment but allowed their detection in traces in the water column, indicating that pheophorbide a steryl esters are, like their pyropheophorbide a analogs, formed in the water column. The distribution of sterols released by hydrolysis of the pheophorbide a steryl esters shows close similarities to that of the free sterols in the water column and of the sterols of the pyropheophorbide a steryl esters. It appears that, like their pyropheophorbide a counterparts, pheophorbide a steryl esters incorporate mainly sterols of phytoplanktonic origin. Their formation probably involves the same mechanism as for pyropheophorbide a steryl ester formation, i.e. metabolism by zooplankton grazing on phytoplankton. The presence of pheophorbide a steryl esters in the oxic sediment and their absence from the anoxic sediment is probably due to a lower stability of compounds containing a carbomethoxy substituent in the anoxic environment.     

Tracking the last sea-level cycle: seafloor morphology and shallow stratigraphy of the latest Quaternary New Jersey middle continental shelf

Seafloor geomorphology and surficial stratigraphy of the New Jersey middle continental shelf provide a detailed record of sea-level change during the last advance and retreat of the Laurentide ice sheet (120 kyr B.P. to Present). A NW–SE-oriented corridor on the middle shelf between water depths of 40 m (the mid-shelf “paleo-shore”) and 100 m (the Franklin “paleo-shore”) encompasses 500 line-km of 2D Huntec boomer profiles (500–3500 Hz), an embedded 4.6 km² 3D volume, and a 490 km² swath bathymetry map. We use these data to develop a relative stratigraphy. Core samples from published studies also provide some chronological and sedimentological constraints on the upper <5 m of the stratigraphic succession.The following stratigraphic units and surfaces occur (from bottom to top): (1) “R”, a high-amplitude reflection that separates sediment >46.5 kyr old (by AMS ¹⁴C dating) from overlying sediment wedges; (2) the outer shelf wedge, a marine unit up to 50 m thick that onlaps “R”; (3) “Channels”, a reflection sub-parallel to the seafloor that incises “R”, and appears as a dendritic system of channels in map view; (4) “Channels” fill, the upper portion of which is sampled and known to represent deepening-upward marine sediments 12.3 kyr in age; (5) the “T” horizon, a seismically discontinuous surface that caps “Channels” fill; (6) oblique ridge deposits, coarse-grained shelly units comprised of km-scale, shallow shelf bedforms; and (7) ribbon-floored swales, bathymetric depressions parallel to modern shelf currents that truncate the oblique ridges and cut into surficial deposits.We interpret this succession of features in light of a global eustatic sea-level curve and the consequent migration of the coastline across the middle shelf during the last 120 kyr. The morphology of the New Jersey middle shelf shows a discrete sequence of stratigraphic elements, and reflects the pulsed episodicity of the last sea-level cycle. “R” is a complicated marine/non-marine erosional surface formed during the last regression, while the outer shelf wedge represents a shelf wedge emplaced during a minor glacial retreat before maximum Wisconsin lowstand (i.e., marine oxygen isotope stage 3.1). “Channels” is a widespread fluvial subarial erosion surface formed at the late Wisconsin glacial maximum 22 kyr B.P. The shoreline migrated back across the mid-shelf corridor non-uniformly during the period represented by “Channels” fill. Oblique ridges are relict features on the New Jersey middle shelf, while the ribbon-floored swales represent modern shelf erosion. There is no systematic relationship between modern seafloor morphology and the very shallowly buried stratigraphic succession.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Decoupling of arsenic and iron release from ferrihydrite suspension under reducing conditions: a biogeochemical model

High levels of arsenic in groundwater and drinking water are a major health problem. Although the processes controlling the release of As are still not well known, the reductive dissolution of As-rich Fe oxyhydroxides has so far been a favorite hypothesis. Decoupling between arsenic and iron redox transformations has been experimentally demonstrated, but not quantitatively interpreted. Here, we report on incubation batch experiments run with As(V) sorbed on, or co-precipitated with, 2-line ferrihydrite. The biotic and abiotic processes of As release were investigated by using wet chemistry, X-ray diffraction, X-ray absorption and genomic techniques. The incubation experiments were carried out with a phosphate-rich growth medium and a community of Fe(III)-reducing bacteria under strict anoxic conditions for two months. During the first month, the release of Fe(II) in the aqueous phase amounted to only 3% to 10% of the total initial solid Fe concentration, whilst the total aqueous As remained almost constant after an initial exchange with phosphate ions. During the second month, the aqueous Fe(II) concentration remained constant, or even decreased, whereas the total quantity of As released to the solution accounted for 14% to 45% of the total initial solid As concentration. At the end of the incubation, the aqueous-phase arsenic was present predominately as As(III) whilst X-ray absorption spectroscopy indicated that more than 70% of the solid-phase arsenic was present as As(V). X-ray diffraction revealed vivianite Fe(II)₃(PO₄)₂.8H₂O in some of the experiments. A biogeochemical model was then developed to simulate these aqueous- and solid-phase results. The two main conclusions drawn from the model are that (1) As(V) is not reduced during the first incubation month with high Eh values, but rather re-adsorbed onto the ferrihydrite surface, and this state remains until arsenic reduction is energetically more favorable than iron reduction, and (2) the release of As during the second month is due to its reduction to the more weakly adsorbed As(III) which cannot compete against carbonate ions for sorption onto ferrihydrite. The model was also successfully applied to recent experimental results on the release of arsenic from Bengal delta sediments.     

XMCD at Fe L<Subscript>2,3</Subscript> edges,Fe and S K edges on Fe<Subscript>7</Subscript>S<Subscript>8</Subscript>

Pyrrhotite (Fe₇S₈) is a natural iron sulphide that can participate in rock magnetisation. Its electronic structure is not yet surely described. X-ray magnetic circular dichroism (XMCD) at Fe L_2,3 edges on Fe₇S₈, coupled with multiplet calculations, shows that iron is present only as Fe²⁺ in this magnetic iron sulphide. It reveals a strong magnetic orbital moment. XMCD at Fe and S K edges shows the quite strong polarization of both Fe and S in Fe₇S₈.     

The MAR-Vema Fracture Zone intersection surveyed by deep submersible Nautile

One of the two objectives of the Vemanaute cruise of the French deep submersible Nautile, was the geological study of the eastern intersection area between the Mid-Atlantic Ridge (MAR) and the Vema Fracture Zone in the equatorial Atlantic. Fourteen dives were conducted that allowed detailed geological survey and sampling of the main morphostructural units of this area: the northern and southern walls of the fracture zone, the median ridge, the northern and southern troughs and the nodal basin. In situ observations of recent tectonic features such as furrows, ridges and circular depressions, concentrated within the southern trough, allowed us to establish the location and the size of the present-day displacement zone. Geological investigations have shown that the nodal basin is entirely floored by basalts thus contrasting with other equivalent areas such as the Kane and Oceanographer fracture zone-MAR eastern intersections. Finally, this study stresses the great opposition between the relatively old and tectonically inactive northern part of the fracture, and the southern part which shows active tectonics and recent volcanic activity.     

Storylines: an alternative approach to representing uncertainty in physical aspects of climate change

Investigating the relationships between climate extremes and crop yield can help us understand how unfavourable climatic conditions affect crop production. In this study, two statistical models, multiple linear regression and random forest, were used to identify rainfall extremes indices affecting wheat yield in three different regions of the New South Wales wheat belt. The results show that the random forest model explained 41–67% of the year-to-year yield variation, whereas the multiple linear regression model explained 34–58%. In the two models, 3-month timescale standardized precipitation index of Jun.–Aug. (SPI_JJA), Sep.–Nov. (SPI_SON), and consecutive dry days (CDDs) were identified as the three most important indices which can explain yield variability for most of the wheat belt. Our results indicated that the inter-annual variability of rainfall in winter and spring was largely responsible for wheat yield variation, and pre-growing season rainfall played a secondary role. Frequent shortages of rainfall posed a greater threat to crop growth than excessive rainfall in eastern Australia. We concluded that the comparison between multiple linear regression and machine learning algorithm proposed in the present study would be useful to provide robust prediction of yields and new insights of the effects of various rainfall extremes, when suitable climate and yield datasets are available.