Molecular environment of iodine in naturally iodinated humic substances: Insight from X-ray absorption spectroscopy

The molecular environment of iodine in reference inorganic and organic compounds, and in dry humic and fulvic acids (HAs and FAs) extracted from subsurface and deep aquifers was probed by iodine L₃-edge X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) of iodine spectra from HAs and FAs resembled those of organic references and displayed structural features consistent with iodine forming covalent bonds with organic molecules. Simulation of XANES spectra by linear combination of reference spectra suggested the predominance of iodine forming covalent bonds to aromatic rings (aromatic-bound iodine). Comparison of extended X-ray absorption fine structure (EXAFS) spectra of reference and samples further showed that iodine was surrounded by carbon shells at distances comparables to those for references containing aromatic-bound iodine. Quantitative analysis of EXAFS spectra indicated that iodine was bound to about one carbon at a distance d (I-C) of 2.01(4)-2.04(9) Å, which was comparable to the distances observed for aromatic-bound iodine in references (1.99(1)-2.07(6) Å), and significantly shorter than that observed for aliphatic-bound iodine (2.15(2)-2.16(2) Å). These results are in agreement with previous conclusions from X-ray photoelectron spectroscopy and from electrospray ionization mass spectrometry. These results collectively suggest that the aromatic-bound iodine is stable in the various aquifers of this study.     

Kernel estimation as a basic tool for geomorphological data analysis

Kernel estimation, based on the convolution of a probability density function with a set of magnitudes or event dates, provides tuneable smooth pictures of probability density functions and event intensity functions. Such pictures are in several respects superior to those provided by histograms, box plots, cumulative distributions or raw plots. They permit examination of broad features and fine structure, are readily produced with modest computational effort and are essentially free of artefacts arising from binning. Examples are given using data on cirque lengths, limestone pavements, glacier areas and dated flood deposits. The technique deserves widespread use in geomorphology and allied sciences. Copyright © 2007 John Wiley & Sons, Ltd.     

Foraging by Two Estuarine Fishes, <Emphasis Type="Italic">Fundulus heteroclitus</Emphasis> and <Emphasis Type="Italic">Fundulus majalis</Emphasis>, on Juvenile Asian Shore Crabs (<Emphasis Type="Italic">Hemigrapsus sanguineus</Emphasis>) in Western Long Island Sound

The Asian shore crab, Hemigrapsus sanguineus, is a recent and particularly successful introduction to the east coast of the USA. Little research has been done on the utilization of Asian shore crabs for food by native species, a potential form of biocontrol. Over a 4-year period, we examined the gut contents of cogeners, Fundulus heteroclitus and Fundulus majalis, collected from two embayments in western Long Island Sound for the presence of juvenile H. sanguineus. Frequency (percent) of occurrence of food items in the guts of both species varied over year and study site. Asian shore crabs were consumed more often by F. heteroclitus than by F. majalis, but predation pressure by both species was low. Only 13% of F. heteroclitus and 7.7% of F. majalis found with food in their guts had ingested Asian shore crab remains. Of those, 1/3 had consumed whole crabs; the rest had only autotomized appendages in their guts. The mean carapace width of juvenile Asian shore crabs ingested by F. heteroclitus was 3.59 ± 2.22 mm (N = 33). Results of our study on killifish predation support the hypothesis that H. sanguienus abundance is partly explained by reduced impact of native predators (i.e., the “enemy release hypothesis”). Predation pressure of other potential enemies on both planktonic and benthic stages of the Asian shore crab must be investigated, however, to understand the full impact of predation on H. sanguineus population dynamics.     

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji.The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C₁, C₂, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found.The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal.An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.     

Relationships between crustal contamination and crystallisation in continental flood basalt magmas with special reference to the Deccan Traps of the Western Ghats, India

The upper part of the Deccan Traps sequence (Bushe to Mahabaleshwar Formations) shows a statistically significant tendency for the most mafic lavas to be the most contaminated by crustal materials. This is the reverse of the relationship shown by suites evolving by contamination accompanied by fractional crystallisation (AFC). The observed correlations (e.g. between Mg-number and Sr isotope initial ratios) are partly an accidental consequence of the fact that the most mafic lavas are more abundant in the lower part of the sequence, while contaminant availability declines in the upper part. It is probable, however, that the correlations are augmented by increased contamination of hotter magma batches during ascent through dykes, a process during which fractional crystallisation is suppressed by magmatic turbulence. The absence of AFC relationships suggests that most of the contamination took place during the ascent stage rather than in a magma chamber. Other continental flood basalt provinces such as the Parana and Etendeka do show AFC relationships, and it is speculated that this may be a result of magma chamber contamination coupled with flow rates which prevent contamination during ascent.     

Magnetic order in grunerite,Fe7Si8O22(OH)2A quasi-one dimensional antiferromagnet with a spin canting transition

Magnetization and neutron diffraction measurements have been made on grunerite, Fe₇Si₈O₂₂(OH)₂, a monoclinic double-chain silicate with Fe²⁺ octahedral bands. The mineral orders antiferromagnetically at 47K into a collinear structure with a second transition at 8K to a canted arrangement. The magnetic susceptibility follows a Curie-Weiss Law above 120K, with a paramagnetic Curie temeprature ?_p=67K. Magnetization measurements below 47K indicate a spin-flop or metamagnetic transition in an applied field of about 12KOe. Powder neutron diffraction measurements between 8–45K reveal that all the Fe²⁺ spins within an octahedral band are ferromagnetically coupled parallel to the b axis, with each band antiferromagnetically coupled to neighboring bands. Below 8K Fe²⁺ spins at the M1 and M4 sites are canted away from the b axis, whereas those at the M2 and M3 sites are not significantly affected. The ordered Fe²⁺ moment on the M4 site is substantially lower than those on the other sites, most likely indicating strong covalency effects, i.e. considerable spin transfer to neighboring oxygen atoms.     

The introduction of the Iau 1980 nutation theory in the computation of the Earth Rotation Parameters by the Bureau International de l'Heure

Summary The status of nutation theory in the computation of the Earth Rotation Parameters from the different observational techniques is reviewed. The impact on the combined solution of the Bureau International de l'Heure is evaluated. In view of the improvement brought by the IAU 1980 Nutation Theory, its introduction in the BIH publications, without waiting for the adoption by the astronomical ephemerides (1984 Jan. 1) is decided.     

Temporal variability in the isotopic niches of rocky shore grazers and suspension‐feeders

Carbon and nitrogen stable isotope ratios were measured in rocky inter‐tidal suspension‐feeders (brown mussels and cape reef worms) and grazers (goat's eye limpets and cape sea urchins) to determine the influences of lifestyle and time on the diets of consumers. Niche partitioning between consumer species within the same feeding guild was assessed using isotopic niche area (a proxy for trophic niche). Specimens were collected monthly at a single site in Southeastern South Africa from July 2010 to June 2011. Temporal variations in isotopic signatures were generally greater in the suspension‐feeders compared with the grazers, isotopic niche widths were smaller in the suspension‐feeders and intra‐population variations in isotope signatures were larger in the grazers. No inter‐specific niche overlap (according to standard ellipse areas) was observed within either feeding guild unless standardization calculations were used. Temporal variations in the diets of all the consumers appeared uncoupled from temporal variability in the isotopic signatures of basal resources in the region; as such, shifts in the consumer diets most likely pertained to feeding behaviour and food preferences. Our data provide new insights into how syntopic rocky shore consumers coexist by partitioning their temporally variable food environment.     

Geology,mineralogy and geochemistry of the Kekem dyke swarm (Western Cameroon): Insights into Paleozoic–Mesozoic magmatism and geodynamic implications

The broadly N70°–90°E-trending dykes swarm at Kekem cut across the Paleoproterozoic-to-Achean terranes of West Cameroon remobilized during the Pan-African orogeny. They are picrite basalts and basalts with tholeiitic/transitional affinity, as shown by mineralogical and geochemical data, with variable major and trace element contents, MgO ranges from 7.3 to 12.4 wt.%, Cr from 190 to 411 ppm, Ni from 15 to 234 ppm. All the dykes are light REE enriched with La_N/Yb_N values of 5.3–8.1, suggesting a co-magmatic origin. They originated from a 2.8% partial melting of a spinel-mantle source with no or little crustal input. The geochemical features of Kekem dykes are similar to those of Paleozoic and Mesozoic dykes recorded in North and Central Africa, suggesting multiple reactivations of pre-existing fractures that resulted in the fragmentation of western Gondwana and the opening of Central and South Atlantic Oceans.