Characterization of a major refractory component of marine dissolved organic matter

Refractory carboxyl-rich alicyclic molecules (CRAM) are characterized in marine dissolved organic matter (DOM) using nuclear magnetic resonance spectroscopy and ultrahigh resolution mass spectrometry. CRAM are distributed throughout the water column and are the most abundant components of deep ocean DOM ever characterized. CRAM are comprised of a complex mixture of carboxylated and fused alicyclic structures with a carboxyl-C:aliphatic-C ratio of 1:2 to 1:7. CRAM are expected to constitute a strong ligand for metal binding, and multiple coordination across cations could promote aggregation and marine gel formation thereby affecting CRAM reactivity and the bioavailability of nutrients and trace metals. It appears CRAM are ultimately derived from biomolecules with structural similarities to sterols and hopanoids. The occurrence of CRAM in freshwater and terrestrial environments seems likely, considering the global distribution of biomolecules and the similarities of biogeochemical processes among environments.     

Calcium-isotope fractionation in selected modern and ancient marine carbonates

The calcium-isotope composition (δ^44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca²⁺_aq-CaCO₃-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition. Biological carbonates generally have lower δ^44/42Ca values than inorganic marine cements, and there appears to be no fractionation between seawater and marine inorganic calcite. A kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against ⁴⁴Ca in biological carbonates when compared to inorganic precipitates. This is supported by a well-defined correlation of the δ^44/42Ca values with Sr concentrations in Cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration. No significant temperature dependence of Ca-isotope fractionation was found in shells of Cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from δ¹⁸O values and Mg concentrations. The reconstruction of secular variations in the δ^44/42Ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and Cretaceous biological carbonates, independent of chemical composition or mineralogy. Despite these variations that may be due to still unidentified biological fractionation mechanisms, the δ^44/42Ca values of Cretaceous skeletal calcite suggest that the δ^44/42Ca value of Cretaceous seawater was 0.3-0.4‰ lower than that of the modern ocean.     

Three-dimensional model and late stage warping of the Plattengneis Shear Zone in the Eastern Alps

The Plattengneis shear zone is a 250–600 m thick, flat lying, Cretaceous, eclogite facies, mylonitic shear zone, with north-over-south transport direction, that is exposed over almost 1000 km² in the Koralpe region along the eastern margin of the Alps. Although the shear zone is one of the largest in the Alps, its role in the Eoalpine metamorphic evolution and the subsequent exhumation of the region, remain enigmatic and its large-scale geometry is not well understood. The outcrop pattern suggests that the shear zone is made up of a single sheet that is folded into a series of open syn- and antiforms with wavelengths of about 10 km. Eclogite bodies occur above, within and below the shear zone and there is no metamorphic grade change across the shear zone. In the south, the fold axes strike east–west and plunge shallowly to the east. In the north, the fold axes are oriented in north–south direction and form a dome shaped structure of the shear zone. Total shortening during this late stage warping event was of the order of 5%. Indirect evidence constrains this folding event to have occurred between 80 and 50 Ma and the fold geometry implies that the final exhumation in the Koralpe occurred somewhat later than further north. Interestingly, the shear zone appears to strike out of the topography in the south and dip into the topography in the north, so that north of the shear zone only hanging-wall rocks are exposed and south of it only foot-wall rocks. Possibilities for the geometric relationship of the Plattengneis shear zone with the surrounding south dipping detachments are discussed.     

Effects of magnetic interactions in anisotropy of magnetic susceptibility: Models, experiments and implications for igneous rock fabrics quantification

Besides granites of the ilmenite series, in which the anisotropy of magnetic susceptibility (AMS) is mainly controlled by paramagnetic minerals, the AMS of igneous rocks is commonly interpreted as the result of the shape-preferred orientation of unequant ferromagnetic grains. In a few instances, the anisotropy due to the distribution of ferromagnetic grains, irrespective of their shape, has also been proposed as an important AMS source. Former analytical models that consider infinite geometry of identical and uniformly magnetized and coaxial particles confirm that shape fabric may be overcome by dipolar contributions if neighboring grains are close enough to each other to magnetically interact. On these bases we present and experimentally validate a two-grain macroscopic numerical model in which each grain carries its own magnetic anisotropy, volume, orientation and location in space. Compared with analytical predictions and available experiments, our results allow to list and quantify the factors that affect the effects of magnetic interactions. In particular, we discuss the effects of (i) the infinite geometry used in the analytical models, (ii) the intrinsic shape anisotropy of the grains, (iii) the relative orientation in space of the grains, and (iv) the spatial distribution of grains with a particular focus on the inter-grain distance distribution. Using documented case studies, these findings are summarized and discussed in the framework of the generalized total AMS tensor recently introduced by Cañon-Tapia (Cañon-Tapia, E., 2001. Factors affecting the relative importance of shape and distribution anisotropy in rocks: theory and experiments. Tectonophysics, 340, 117–131.). The most important result of our work is that analytical models far overestimate the role of magnetic interaction in rock fabric quantification. Considering natural rocks as an assemblage of interacting and non-interacting grains, and that the effects of interaction are reduced by (i) the finite geometry of the interacting clusters, (ii) the relative orientation between interacting grains, (iii) their heterogeneity in orientation, shape and bulk susceptibility, and (iv) their inter-distance distribution, we reconcile analytical models and experiments with real case studies that minimize the role of magnetic interaction onto the measured AMS. Limitations of our results are discussed and guidelines are provided for the use of AMS in geological interpretation of igneous rock fabrics where magnetic interactions are likely to occur.     

Variscan to eo-Alpine events recorded in European lower-crust zircons sampled from the French Massif Central and Corsica, France

Ion-microprobe U–Pb zircon dating of lower-crust metasedimentary granulite are reported on samples from two localities in Europe in order to determine (a) how this environment recorded the Variscan and eo-Alpine events, and (b) whether the transition between the two orogenic cycles was continuous or separated by a gap. The samples come from enclaves hosted by Miocene volcanoes at Bournac in the French Massif Central, and from the granulitic metasedimentary basement of the Alpine Santa Lucia nappe in Corsica, on the South European paleomargin of the Ligurian branch of the Tethys Sea. The zircon ages from Bournac range between 630 and 430 Ma and between 380 and 150 Ma with a major frequency peak at 285 Ma; the zircons older than 430 Ma are interpreted as detrital, whereas those younger than 380 Ma are considered to have formed by metamorphic processes after burial in the lower crust. Zircon ages from Santa Lucia range from to 356 to 157 Ma, with exception of one inherited Archean grain, and are interpreted like the younger Bournac zircons as having been formed by metamorphic processes.

In a granulite metamorphic environment, as opposed to an anatectic environment, new zircon growth can occur in the solid state. Once Zr has been incorporated into zircon, however, it is difficult to remobilize without dissolution; thus Zr available for new zircon growth must result from the breakdown of Zr-bearing minerals during prograde and/or retrograde events. In this light, the U–Pb zircon-age probability curves are interpreted as markers for major tectonometamorphic events, as suggested by the close correspondence between peaks in the curve and geological events recorded in the upper-crust, such as magma emplacement and basin subsidence.

Evidence of a tectonometamorphic gap between the Variscan and Alpine orogeneses is provided by the Santa Lucia zircon-age probability curve, which reveals a probable interlude during the Variscan–Alpine transition between 240 and 210 Ma. Here, the peak at 240 Ma is interpreted as the very beginning of crustal extension and the low at 210 Ma as a period of quiescence prior to the formation of an active margin and oceanization.     

The transition from peraluminous to peralkaline granitic melts: Evidence from melt inclusions and accessory minerals

Fractional crystallization of peraluminous F- and H₂O-rich granite magmas progressively enriches the remaining melt with volatiles. We show that, at saturation, the melt may separate into two immiscible conjugate melt fractions, one of the fractions shows increasing peraluminosity and the other increasing peralkalinity. These melt fractions also fractionate the incompatible elements to significantly different degrees. Coexisting melt fractions have differing chemical and physical properties and, due to their high density and viscosity contrasts, they will tend to separate readily from each other. Once separated, each melt fraction evolves independently in response to changing T/P/X conditions and further immiscibility events may occur, each generating its own conjugate pair of melt fractions. The strongly peralkaline melt fractions in particular are very reactive and commonly react until equilibrium is attained. Consequently, the peralkaline melt fraction is commonly preserved only in the isolated melt and mineral inclusions.

We demonstrate that the differences between melt fractions that can be seen most clearly in differing melt inclusion compositions are also visible in the composition of the resulting ore-forming and accessory minerals, and are visible on scales from a few micrometers to hundreds of meters.     

Geochemistry of silicic magmas in the Macolod Corridor, SW Luzon, Philippines: evidence of distinct, mantle-derived, crustal sources for silicic magmas

Silicic volcanic deposits (>65 wt% SiO₂), which occur as domes, lavas and pyroclastic deposits, are relatively abundant in the Macolod Corridor, SW Luzon, Philippines. At Makiling stratovolcano, silicic domes occur along the margins of the volcano and are chemically similar to the silicic lavas that comprise part of the volcano. Pyroclastic flows are associated with the Laguna de Bay Caldera and these are chemically distinct from the domes and lavas at Makiling stratovolcano. As a whole, samples from the Laguna de Bay Caldera contain lower concentrations of MgO and higher concentrations of Fe₂O_3(t) than the samples from domes and lavas. The Laguna de Bay samples are more enriched in incompatible trace elements. The silicic rocks from the domes, Makiling Volcano and Laguna de Bay Caldera all contain high alkalis and high K₂O/Na₂O ratios. Melting experiments of primitive basalts and andesites demonstrate that it is difficult to produce high K₂O/Na₂O silicic magmas by fractional crystallization or partial melting of a low K₂O/Na₂O source. However, recent melting experiments (Sisson et al., Contrib Mineral Petrol 148:635–661, 2005) demonstrate that extreme fractional crystallization or partial melting of K-rich basalts can produce these silicic magmas. Our model for the generation of the silicic magmas in the Macolod Corridor requires partial melting of mantle-derived, evolved, moderate to K-rich, crystallized calc-alkaline magmas that ponded and crystallized in the mid-crust. Major and trace element variations, along with oxygen isotopes and ages of the deposits, are consistent with this model. Electronic Supplementary Material Supplementary material is available for this article at     

Distribution of cadmium, chromium, copper, lead and zinc in marine sediments in Hong Kong waters

Partitioning of heavy metals (Cd, Cr, Cu, Pb, Zn) in marine sediments collected from various sites in Hong Kong waters were determined using sequential extraction method. Sediments from Kellette Bank, located in Victoria Harbour, had higher metal concentrations especially Cu and Zn than most other sites. Slightly over 20% of total Cu and Cr existed as readily available forms in Peng Chau and Kellette Bank. At most sampling sites, over 15% of the Cu existed as the exchangeable form indicating that Cu could be readily released into the aqueous phase from sediments. A significantly higher percentage of Pb and Zn was associated with the three non-residual fractions. Hence, there is a greater environmental concern for remobilization of Pb and Zn compared with Cr. The high amount of residual Cd (>50%) and the relatively lower Cd content indicate that little environmental concern is warranted for the remobilization of Cd. Distribution of metals in sediments collected from different depth at Kellette Bank shows that metal concentrations decreased with profile depth. The levels of Pb and Zn associated with the two readily available fractions increased sharply in the surface sediment. These metals represented the pollutants, which were introduced into the area in the mid-eighties through early nineties as a result of rapid economic and industrial development in the territory. As significant portions of these metals were bound to the readily available phases in the surface sediments, metal remobilization could be a concern. An erratum to this article can be found at     

Unequal Competition Among Chains of Supercenters: Kmart,Target, and Wal‐Mart

The three largest discount chains, Kmart, Target, and Wal‐Mart, have adopted the supercenter format for expansion. This article examines the locations of and the competition among these supercenters. Wal‐Mart has the greatest number of supercenters and is driving the expansion of the supercenter format. Both Kmart and Target have clustered their supercenters in a small number of metropolitan markets. In contrast to Wal‐Mart and Kmart, Target has focused on a middle‐class rather than a blue‐collar clientele. Now Kmart is struggling following a declaration of bankruptcy. Wal‐Mart has largely defeated its supercenter competitors and now is confronting the major grocery chains for grocery sales.