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.     

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.     

Crustal structure across the Grand Banks–Newfoundland Basin Continental Margin – II. Results from a seismic reflection profile

New multichannel seismic reflection data were collected over a 565 km transect covering the non-volcanic rifted margin of the central eastern Grand Banks and the Newfoundland Basin in the northwestern Atlantic. Three major crustal zones are interpreted from west to east over the seaward 350 km of the profile: (1) continental crust; (2) transitional basement and (3) oceanic crust. Continental crust thins over a wide zone (∼160 km) by forming a large rift basin (Carson Basin) and seaward fault block, together with a series of smaller fault blocks eastwards beneath the Salar and Newfoundland basins. Analysis of selected previous reflection profiles (Lithoprobe 85-4, 85-2 and Conrad NB-1) indicates that prominent landward-dipping reflections observed under the continental slope are a regional phenomenon. They define the landward edge of a deep serpentinized mantle layer, which underlies both extended continental crust and transitional basement. The 80-km-wide transitional basement is defined landwards by a basement high that may consist of serpentinized peridotite and seawards by a pair of basement highs of unknown crustal origin. Flat and unreflective transitional basement most likely is exhumed, serpentinized mantle, although our results do not exclude the possibility of anomalously thinned oceanic crust. A Moho reflection below interpreted oceanic crust is first observed landwards of magnetic anomaly M4, 230 km from the shelf break. Extrapolation of ages from chron M0 to the edge of interpreted oceanic crust suggests that the onset of seafloor spreading was ∼138 Ma (Valanginian) in the south (southern Newfoundland Basin) to ∼125 Ma (Barremian–Aptian boundary) in the north (Flemish Cap), comparable to those proposed for the conjugate margins.     

Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

Single frequency processing of Ørsted GPS radio occultation measurements

The Global Positioning System (GPS) radio occultation measurements obtained using the TurboRogue GPS receiver on the Danish satellite Ørsted have been processed using the single frequency method. Atmospheric profiles of refractivity and temperature are derived and validated against numerical weather prediction data from the European Centre for Medium-Range Weather Forecast (ECMWF). Results from the Ørsted GPS measurement campaign in February 2000 indicate that the single frequency method can provide retrievals with accuracy comparable to that of using two frequencies. From comparisons between measured dry temperature profiles and corresponding dry temperature profiles derived from ECMWF analysis fields, we find a mean difference of less than 0.5 K and a standard deviation of 2–4 K between 500 and 30 hPa in height. Above 30 hPa the impact of the ionosphere becomes more dominant and more difficult to eliminate using the single frequency method, and the results show degraded accuracy when compared to previous analysis results of occultation data from other missions using the dual frequency method. At latitudes less than 40° (denoted low latitudes), the standard deviation is generally smaller than at latitudes higher than 40° (denoted high latitudes). A small temperature bias is observed centered at 200 hPa for low latitudes and at 300 hPa for high latitudes. This indicates that the ECMWF analyses do not adequately resolve the tropopause temperature minimum. In the lowest part of the troposphere an observed warm bias is thought to be due to erroneous tracking of the GPS signal in cases of atmospheric multipath propagation.     

FORMOSAT-3/COSMIC science mission update

The FORMOSAT-3/COSMIC mission is a microsatellite mission for weather forecast, climate monitoring, and atmospheric, ionospheric and geodesy research. This mission is a collaborative Taiwan-USA science experiment to deploy a constellation of six microsatellites in low Earth orbits. The mission life is 2 years with a goal of 5 years. The final mission orbit has an altitude of 750–800 km. Each satellite consists of three science payloads: global positioning system (GPS) occultation experiment (GOX) payload, tiny ionospheric photometer (TIP) and tri-band beacon (TBB). The GOX will collect the GPS signals for the study on atmosphere, ionosphere, and geodesy. The TIP and TBB can provide the electron distribution information for ionospheric research. The deployment of the FORMOSAT-3 constellation and the resulting influence on the occultation sounding distributions are reported. Details are also given on GOX, TIP, and TBB payload operations and the contributions of the Taiwan Science Team.